ARRAY FOR PROCESSING MATERIALS

RESEAU DE TRAITEMENT DE MATIERES

English Abstract

Materials (e.g., plant biomass, animal biomass, and municipal waste biomass) are processed to produce useful intermediates and products, such as energy, fuels, foods or materials. For example, systems equipment, and methods are described that can be used to treat feedstock materials, such as cellulosic and/or lignocellulosic materials, using an array of vaults.

French Abstract

Selon l'invention, des matières (de la biomasse végétale, de la biomasse animale et de la biomasse issue de déchets urbains, par exemple) sont traités pour produire des intermédiaires et des produits utiles, tels que de l'énergie, des carburants, des aliments ou divers matériaux. L'invention concerne, par exemple, des équipements, des systèmes et des procédés pouvant servir à traiter des matières de charge, telles que des matières cellulosiques et/ou lignocellulosiques, au moyen d'un réseau d'enceintes.

Claims

CLAIMS
1. A treatment operating unit, comprising:
a plurality of enclosure systems, each enclosure system including one or more
vaults, and
within each vault, an irradiation device and a treatment conveyor.
2. The operating unit of claim 1, wherein the enclosure systems are arranged
in
rows.
3. The operating unit of claim 2, wherein the rows extend in a first
direction, and
wherein each enclosure system comprises two or more vaults extending in a
direction
generally perpendicular to the first direction.
4. The operating unit of claim 3, wherein the first and second vaults of each
enclosure share a common wall.
5. The operating unit of claim 4, wherein each first vault is configured to
accept
untreated biomass from a storage facility, and wherein the biomass material is
treated in
each vault utilizing the irradiation device and the treatment conveyor.
6. The operating unit of claim 5, wherein the first vault of each enclosure
system
further encloses equipment configured to transfer treated biomass from the
first vault to
the second vault of the enclosure system.
7. The operating unit of any one of the previous claims, wherein the
irradiation
device comprises an electron accelerator.
8. The operating unit of any one of the previous claims, wherein the treatment
conveyor comprises a vibratory conveyor.
9. A method for producing treated materials, the method comprising;
partitioning a material into a plurality of material portions,
conveying the material portions into a plurality of first vaults, each first
vault
accepting one of the material portions,
treating the material portions in the vaults,

conveying the material portions out of the first vaults, and
combining the material portions.
10. The method of claim 9, wherein treating comprises a treatment method
selected from the group consisting of dosing with ionizing radiation,
sonication,
oxidation, pyrolysis, steam explosion, chemical treatment, mechanical
treatment, freeze
grinding and combinations thereof.
11. The method of claim 10, wherein dosing with ionizing radiation comprises
irradiation with an electron beam.
12. The method of claim 10 or 11, wherein each material portion is treated
with a
dose between about 10 Mrad and about 150 Mrad of radiation.
13. The method of any one of claims 10 through 12, wherein within each first
vault the material is treated with a dose between about 10 and about 50 Mrad
of
radiation.
14. The method of any one of claims 9 through 13, wherein each conveying step
comprises pneumatically conveying.
15. The method of any one of claims 9 through 14, further comprising conveying
the material with a vibratory conveyor while treating the material portions.
16. The method of any one of claims 9 through 15, further comprising
continuously partitioning the material, continuously conveying the material
portions into
the first vaults, continuously treating the material portions and continuously
combining
the material portions, to continuously produce a treated material.
17. The method of any one of claims 9 through 16, wherein the temperature of
each material portion does not exceed 150 °C during the treating step.
18. The method of any one of claims 9 through 17, further comprising cooling
each material portion while treating and/or cooling between irradiations
(e.g., utilizing a
screw cooler).
19. The method of any one of claims 9 through 18, further comprising, after
conveying the material portions out of the first vaults, conveying the
material portions to
a plurality of second vaults, each second vault accepting one of the material
portions,
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treating the material portions in the second vaults,
conveying the material portions out of the second vaults.
20. The method of claim 19, wherein each first and second vaults share a
common wall.
21. The method of claim 19 or 20, further comprising cooling the material
portions between the first treating step and second treating step.
22. The method of any one of claims 9 through 21, wherein the material is a
biomass material and treating reduces or further reduces the recalcitrance of
the biomass
material.
23. The method of claim 22, wherein the biomass material is a cellulosic or
lignocellulosic material.
24. The method of claim 23, wherein the cellulosic or lignocellulosic biomass
is
selected from ihe group consisting of paper, paper products, paper waste,
paper pulp,
pigmented papers, loaded papers, coated papers, filled papers, magazines,
printed matter,
printer paper, polycoated paper, card stock, cardboard, paperboard, cotton,
wood, particle
board, forestry wastes, sawdust, aspen wood, wood chips, grasses, switchgrass,
miscanthus, cord grass, reed canary grass, grain residues, rice hulls, oat
hulls, wheat
chaff, barley hulls, agricultural waste, silage, canola straw, wheat straw,
barley straw, oat
straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn
stover, soybean
stover, corn fiber, alfalfa, hay, coconut hair, sugar processing residues,
bagasse, beet
pulp, agave bagasse, algae, seaweed, manure, sewage, arracacha, buckwheat,
banana,
barley, cassava, kudzu, ocra, sago, sorghum, potato, sweet potato, taro,
yarns, beans,
favas, lentils, peas, and mixtures of any of these.
25. The method of any one of claims 9 through 24, wherein the treated material
is
produced at a rate of at least 500 1b/hr per vault.
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Description

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ARRAY FOR PROCESSING MATERIALS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from the following provisional
applications:;
USSN 61/774,684, filed March 8, 2013; USSN 61/774,773, filed March 8, 2013;
USSN
61/774,731, filed March 8, 2013; USSN 61/774,735, filed March 8, 2013; USSN
61/774,740, filed March 8, 2013; USSN 61/774,744, filed March 8, 2013; USSN
61/774,746, filed March 8, 2013; USSN 61/774,750, filed March 8, 2013; USSN
61/774,752, filed March 8, 2013; USSN 61/774,754, filed March 8, 2013; USSN
61/774,775, filed March 8, 2013; USSN 61/774,780, filed March 8, 2013; USSN
61/774,761, filed March 8, 2013; USSN 61/774,723, filed March 8, 2013; and
USSN
61/793,336, filed March 15, 2013. The full disclosure of each of these
provisional
applications is incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] Many potential lignocellulosic feedstocks are available today,
including
agricultural residues, woody biomass, municipal waste, oilseeds/cakes and
seaweed, to
name a few. At present, these materials are often under-utilized, being used,
for
example, as animal feed, biocompost materials, burned in a co-generation
facility or even
landfilled.
[0003] Lignocellulosic biomass includes crystalline cellulose fibrils
embedded in a
hemicellulose matrix, surrounded by lignin. This produces a compact matrix
that is
difficult to access by enzymes and other chemical, biochemical and/or
biological
processes. Cellulosic biomass materials (e.g., biomass material from which the
lignin
has been removed) is more accessible to enzymes and other conversion
processes, but
even so, naturally-occurring cellulosic materials often have low yields
(relative to
theoretical yields) when contacted with hydrolyzing enzymes. Lignocellulosic
biomass
is even more recalcitrant to enzyme attack. Furthermore, each type of
lignocellulosic
biomass has its own specific composition of cellulose, hemicellulose and
lignin.
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SUMMARY
[0004] Generally, the inventions relate to enclosures for treating
materials, such as
biomass materials. This inventions also relate to equipment, methods and
systems for
producing products, e.g., from a biomass material. The methods and systems
include
utilizing an array of vaults for processing the biomass material. Generally,
many
methods include treating recalcitrant biomass in vaults with electron beams
and then
biochemically and chemically processing the reduced recalcitrance material to,
for
example, ethanol, xylitol and other products.
[0005] In one aspect, the invention relates to a method of producing
treated
materials, such as biomass materials or hydrocarbon-containing materials,
include
partitioning the materials into a plurality of portions; conveying the
portions into a
plurality of vaults, each vault accepting one of the portions; treating the
material portions
in the vaults, (e.g., to reduce the recalcitrance of biomass portions);
conveying the
portions out of the vaults; and combining the material portions.
[0006] In another aspect, the invention relates to methods of producing
treated
materials, (e.g., treated biomass material, treated hydrocarbon containing
material) the
method including partitioning the material into a plurality of material
portions,
conveying the portions into a plurality of first vaults wherein each first
vault accepts one
portion of the material portions. The portions are then treated in each of the
first vaults
(e.g., if the material is a biomass it is treated to reduce the recalcitrance
of the biomass).
After this treatment, the material portions are conveyed out of the first
vaults and
combined, producing a combined treated material. The treatment can be selected
from
the group consisting of dosing with ionizing radiation, sonication, oxidation,
pyrolysis,
steam explosion, chemical treatment, mechanical treatment, freeze grinding and
combinations of these. Optionally, the irradiation can be with an electron
beam, for
example, with a dosage of between about 10 and about 150 Mrad of radiation
(e.g.,
treating in the first vault with between about 10 and about 50 Mrad of
radiation, or with
between about 5 and about 20 Mrad). The material can be conveyed (e.g., into,
out of
and/or through the vaults) pneumatically. Optionally, the material is conveyed
with a
vibratory conveyor while treating the material portions.
[0007] In some implementations the steps in the method are continuous so
that the
method continuously produces a treated material. For example, in the methods
the
material is continuously partitioned, the material portions are continuously
conveyed into
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the first vaults, the material portions are continuously treated and the
treated material
portions are continuously conveyed out of the first vaults and continuously
combined.
[0008] In some implementation the temperature of each material portion
does not
exceed about 150 C during the treating step. For example, optionally, each
material
portion can be cooled while treating the material, or cooled before or after
treating the
material, e.g., the material can be cooled between treatments with a screw
cooler. The
treated material can be produced at a rate of at least 500 lb/hr per vault
(e.g., more than
about 1,0001b/hr per vault, more than about 15001b/hr per vault, more than
about
2,0001b/hr per vault, more than about 2,5001b/hr per vault, more than about
3,0001b/hr
per vault, more than about 3,5001b/hr per vault, more than about 4,0001b/hr
per vault,
more than about 4,5001b/hr per vault). Optionally, processing of the material
occurs at a
rate of between about 1,000 lb per hour and about 10,000 lb per hour, such as
between
about 2,000 lb per hour and about 6,000 lb per hour or between about 2,000 lb
per hour
and about 5,000 lbs per hour. Optionally, the processing can even be greater
than about
10,000 lb per hour, such as greater than about 15,000 lb per hour, greater
than about
20,000 lb per hour, greater than about 25,000 lb per hour. For example, the
material can
be conveyed through a vault at a rate of between about 1,000 lb per hour and
about
10,000 lb per hour, between about 2,000 lb per hour and about 6,000 lb per
hour,
between about 2,000 lb per hour and about 5,000 lb per hour. Optionally, the
material
can be conveyed through the enclosures (e.g., while being treated) at a rate
greater than
about 10,000 lb per hour, greater than about 15,000 lb per hour, greater than
about
20,000 lb per hour, or even greater than about 25,000 lb per hour.
[0009] In some implementations, the method further includes, after
conveying the
material portions out of the first vaults, conveying the material portions to
a plurality of
second vaults, the second vaults accepting one of the material portions. In
this
implementation, the material portions can be treated, for example, by
irradiation with an
electron beam, or any of the other methods mentioned (e.g., ionizing
radiation,
sonication, oxidation, pyrolysis, steam explosion, chemical treatment,
mechanical
treatment, freeze grinding and combinations of these). For example, if the
material is a
biomass, treatment in the second vault can further reduce the biomass
recalcitrance. For
example, the treatment in the second vault can deliver a dose of between about
1 and
about 100 Mrads (e.g., between about 5 and about 20 Mrad of radiation) to the
material.
After this second treatment, the material portions can be conveyed out of the
second
vaults and combined. Optionally, the first and second vaults share a common
wall.
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Optionally the material portions can be cooled between the first treating step
and the
second treating step.
[0010] As disclosed previously, in some implementations the material is
a biomass
material that includes cellulosic or lignocellulosic materials. The treatment
can reduce or
further reduce the recalcitrance of the biomass. For example the material can
be selected
from the group consisting of paper, paper products, paper waste, paper pulp,
pigmented
papers, loaded papers, coated papers, filled papers, magazines, printed
matter, printer
paper, polycoated paper, card stock, cardboard, paperboard, cotton, wood,
particle board,
forestry wastes, sawdust, aspen wood, wood chips, grasses, switchgrass,
miscanthus,
cord grass, reed canary grass, grain residues, rice hulls, oat hulls, wheat
chaff, barley
hulls, agricultural waste, silage, canola straw, wheat straw, barley straw,
oat straw, rice
straw, jute, hemp, flax, bamboo, sisal, abaca, corn cobs, corn stover, soybean
stover, corn
fiber, alfalfa, hay, coconut hair, sugar processing residues, bagasse, beet
pulp, agave
bagasse, algae, seaweed, manure, sewage, arracacha, buckwheat, banana, barley,
cassava, kudzu, ocra, sago, sorghum, potato, sweet potato, taro, yams, beans,
favas,
lentils, peas and combinations of these.
[0011] In another aspect, the invention relates to a treatment operating
unit that
includes a plurality of enclosure systems, each enclosure system including one
or more
vaults, each vault has within it an irradiation device (e.g., an electron
accelerator) and a
treatment conveyor (e.g., a vibratory conveyor). Optionally the enclosure
systems can be
arranged in rows, for example, extending in a first direction, wherein each
enclosure
system includes two or more vaults (e.g., a first vault and a second vault)
extending in a
direction generally perpendicular to the first direction.
[0012] In some implementations, for example, such as when the enclosures
include a
first and second vault, each enclosure can share a common wall. Optionally
each first
vault is configured to accept untreated biomass from a storage facility,
wherein the
biomass material is treated in each vault utilizing the irradiation device and
the treatment
conveyor (e.g., a vibratory conveyor). Additionally, each first vault of each
enclosure
system further encloses equipment configured to transfer treated biomass from
each first
vault to each second vault of the enclosure system.
[0013] A limitation of treatment of biomass by irradiation is that in
some cases
where treatment, for example recalcitrance reducing treatment, requires a
specific dosage
throughout the material, if one or two treatment vaults are utilized, the
throughput can be
very low. Utilizing an array of vaults, in which each vault is equipped with
an irradiation
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device, can greatly increase the throughput. Additionally, if the arrays are
joined so as to
use common walls, the construction material costs can be greatly reduced.
[0014] Implementations of the invention can optionally include one or
more of the
following summarized features. In some implementations, the selected features
can be
applied or utilized in any order while in other implementations a specific
selected
sequence is applied or utilized. Individual features can be applied or
utilized more than
once in any sequence and even continuously. In addition, an entire sequence,
or a portion
of a sequence, of applied or utilized features can be applied or utilized
once, repeatedly
or continuously in any order. In some optional implementations, the features
can be
applied or utilized with different, or where applicable the same, set or
varied,
quantitative or qualitative parameters as determined by a person skilled in
the art. For
example, parameters of the features such as size, individual dimensions (e.g.,
length,
width, height), location of, degree (e.g., to what extent such as the degree
of
recalcitrance), duration, frequency of use, density, concentration, intensity
and speed can
be varied or set, where applicable as determined by a person of skill in the
art.
[0015] Features, for example, include: a treatment operating unit
including a
plurality of enclosure systems; enclosure systems including one or more
vaults; vaults
have with them an irradiation device and a treatment conveyor; enclosure
systems that
are arranged in rows; enclosure systems arranged in rows extending in a first
direction
and the enclosure systems include two or more vaults extending in a direction
generally
perpendicular to the first direction; enclosures that include a shared wall
between a first
and second vault within the enclosure; an enclosure system with a first vault
configured
to accept untreated biomass from a storage facility; vaults configured for
treating
biomass material therein utilizing an irradiation device and a treatment
conveyor in the
vaults; equipment in an enclosure system configured to transfer treated
biomass from a
first vault of the enclosure system to a second vault of the enclosure system;
an
irradiation device in a vault of an enclosure system configured for
irradiation of material
in the vault; a conveyer or conveyor system that includes a vibratory conveyor
enclosed
in a vault.
[0016] Features, for example, also can include: a method for producing
treated
materials that include partitioning a material into a plurality of material
portions;
conveying a plurality of material portions into a plurality of first vaults,
each first vault
accepting one of the material portions; treating a material portion in a first
vault;
conveying a material portion out of a first vault; combining material portions
that have
been conveyed out of a plurality of first vaults; treating materials with
ionizing radiation;

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treating materials by sonication; treating materials by oxidation; treating
materials by
pyrolysis; treating materials by steam explosion; treating materials by
chemical
treatment; treating materials by mechanical treatment; treating materials by
freezing;
treating materials with an electron beam; treating material with a dose of
between about
and about 150 Mrad of radiation; treating material with a dose of between
about 10
and about 50 Mrad of radiation; a material is conveyed in a conveying step
including
pneumatically conveying; a material portion is conveyed with a vibratory
conveyor in a
vault while the portion is treated in the vault; continuously partitioning a
material;
continuously conveying a material portions into first vaults; continuously
treating
material portions and continuously combining material portions; continuously
producing
treated material; the temperature of a material portion does not exceed 150 C
during a
treating step; cooling of a material portion while treating the material
portion; utilizing a
first and second vault sharing a common wall; cooling a material portion
between a first
treating step and a second treating step; treating a biomass material to
reduce or further
reduce its recalcitrance; treating a cellulosic or lignocellulosic material to
reduce or
further reduce its recalcitrance; treating material that includes paper;
treating material
that includes paper products; treating material that includes paper waste;
treating material
that includes paper pulp; treating material that includes pigmented papers;
treating
material that includes loaded papers; treating material that includes coated
papers;
treating material that includes filled papers; treating material that includes
magazines;
treating material that includes printed matter; treating material that
includes printer
paper; treating material that includes polycoated paper; treating material
that
includes card stock; treating material that includes cardboard; treating
material that
includes paperboard; treating material that includes cotton; treating material
that
includes wood; treating material that includes panicle board; treating
material that
includes forestry wastes; treating material that includes sawdust; treating
material that
includes aspen wood; treating material that includes wood chips; treating
material that
includes grasses; treating material that includes switchgrass; treating
material that
includes miscanthus; treating material that includes cord grass; treating
material that
includes reed canary grass; treating material that includes grain residues;
treating
material that includes rice hulls; treating material that includes oat hulls;
treating material
that includes wheat chaff; treating material that includes barley hulls;
treating material
that includes agricultural waste; treating material that includes silage;
treating material
that includes canola straw; treating material that includes wheat straw;
treating material
that includes barley straw; treating material that includes oat straw;
treating material that
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includes rice straw treating material that includes jute; treating material
that includes
hemp treating material that includes flax; treating material that includes
bamboo treating
material that includes sisal; treating material that includes abaca; treating
material that
includes corn cobs treating material that includes corn stover; treating
material that
includes soybean stover treating material that includes corn fiber; treating
material that
includes alfalfa; treating material that includes hay; treating material that
includes
coconut hair; treating material that includes sugar processing residues;
treating material
that includes bagasse treating material that includes beet pulp; treating
material that
includes agave bagasse; treating material that includes algae; treating
material that
includes seaweed; treating material that includes manure; treating material
that includes
sewage; treating material that includes arracacha; treating material that
includes
buckwheat; treating material that includes banana; treating material that
includes barley;
treating material that includes cassava treating material that includes kudzu
treating
material that includes oera treating material that includes sago; treating
material that
includes sorghum; treating material that includes potato treating material
that includes
sweet potato; treating material that includes taro; treating material that
includes yams;
treating material that includes beans; treating material that includes favas;
treating
material that includes lentils; treating material that includes peas; treating
material that is
produced by processing through a plurality of vaults at a rate of at least 500
lb/hr per
vault,
[0017] Other features and advantages of the invention will be apparent
from the
following detailed description, and from the claims.
DESCRIPTION OF THE DRAWING
[0018] FIG. 1 is a flow diagram showing processes for manufacturing
sugar
solutions and products derived therefrom.
[0019] FIG. 2 is a diagram showing a process for treating a biomass.
[0020] FIG. 3A is a perspective view of an array for biomass treatment.
FIG. 3B is a
top side view of the array for biomass treatment showing a possible flow path
for the
biomass. FIG. 3C is a detailed view of the array, showing four vaults sharing
a common
wall.
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DETAILED DESCRIPTION
[0021] Using the methods and systems described herein, cellulosic and
lignocellulosic feedstock materials, for example, that can be sourced from
biomass (e.g.,
plant biomass, animal biomass, paper, and municipal waste biomass) and that
are often
readily available but difficult to process, can be turned into useful products
(e.g., sugars
such as xylose and glucose, and alcohols such as ethanol and butanol).
Included are
methods and systems for treating materials (e.g., biomass and hydrocarbon
containing
materials) utilizing an array of vaults.
[0022] Referring to FIG. 1, processes for manufacturing sugar solutions
and products
include, for example, optionally mechanically treating a cellulosic and/or
lignocellulosic
feedstock 110. Before and/or after this treatment, the feedstock can be
treated with
another physical treatment, for example irradiation, to reduce or further
reduce its
recalcitrance 112. A sugar solution is formed by saccharifying the feedstock
114 by, for
example, the addition of one or more enzymes 111. A product can be derived
from the
sugar solution, for example, by fermentation to an alcohol 116. Further
processing 124
can include purifying the solution, for example by distillation. If desired,
the steps of
measuring lignin content 118 and setting or adjusting process parameters based
on this
measurement 120 can be performed at various stages of the process, for
example, as
described in U.S. Patent No. 8,415,122 issued April 9, 2013, the complete
disclosure of
which is incorporated herein by reference.
[0023] The treatment step 112 can be irradiation with an electron beam.
An
advantageous method for increasing the throughput of the treatment and more
evenly
spreading out total treatment levels is represented in FIG. 2. In this method
a biomass
material e.g., an untreated biomass material, is portioned into a plurality of
biomass
portions (or rows), for example 1, 2, 3 up to N portions (or rows). The
portions or rows
of biomass are sent to N rows of vaults, where each row of vaults can include
1, 2, 3...up
to M vaults (e.g., 1, 2, 3...up to M columns of vaults). In such an
embodiment, e.g.,
biomass, can be treated to a desired total treatment level by the application
of a number
of smaller treatment levels. This can be useful, e.g., if the material cannot
withstand the
temperature rise of the total treatment level, but can withstand the
temperature rise
associated with a lower treatment level. The number of rows can be between 1
to 100
(e.g., 2 to 50, 3 to 30, 4 to 20 or 10 to 20). The number of columns of vaults
can be
between 1 to 10 (e.g., between 1 to 6, between 2 to 6, or between 2 to 4.
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[0024] In an alternative to the method depicted in FIG. 2, the biomass
in one portion
(or row) can be treated in vaults in different rows. For example, this could
include
diverting the biomass from Vault (1, 1) to Vault (2, 2) and then to Vault (N,
4). Diverting
the biomass portion in this way can be useful to avoid particular vaults if
they are not
operational (e.g., they are being repaired, they are under maintenance or they
are not
needed).
[0025] FIG. 3A is a perspective view showing an embodiment of a
treatment array
and some associated systems. A possible flow path is indicated by arrows for
the
biomass through the system. FIG. 3B is a top side view of this embodiment.
This
embodiment includes an array of 9 by 2 treatment vaults 302 or 9 rows by 2
columns,
where rows 1, 2 and 3 are labeled as R1, R2 and R3. The vaults are contained
within the
frame of an enclosure 303. The biomass feed is pneumatically transported
through tube
304 to an inlet at the top of elevator house 306. The elevator house contains
equipment to
send the biomass to the pre-process storage silos 308. For example, the
elevator house
can contain bag houses and various conveyors and elevators. Elevator house 306
also
contains equipment to deliver the biomass from the storage silos 308 to the
array of
treatment vaults 302. In the example shown in FIG. 3B, the biomass is
delivered
pneumatically through a tube 310 that is functionally connected to (e.g.,
fluidly
connected, in pneumatic connection with) tubes 312 and, which are in fluid
communications with inlets 314, which deliver biomass to the 9 vaults which
are the first
in each column (vaults 316). These inlets may extend through the walls (as
shown) or
ceiling of the associated vaults.
[0026] Portions of biomass are fed to each of the vaults 316 for
irradiation treatment,
as discussed above. During each irradiation treatment, systems including
conveyors can
convey the biomass in each unit under irradiation devices (e.g., including a
scan horn and
electron beam accelerator). Part of the irradiation device is mounted above
the vaults,
for example, electron beam equipment 320 and 322. Treating biomass in this
fashion,
e.g., allows biomass to be treated to a high total level, e.g., 30-50 Mrad, in
two equal
installments, e.g., 15-25 Mrad each, which prevents biomass from overheating.
For
example, the adiabatic temperature rise (AT) from adsorption of ionizing
radiation is
given by the equation: AT = D/Cp : where D is the average dose in kGy, Cp is
the heat
capacity in J/g C, and AT is the change in temperature in C. A typical dry
biomass
material will have a heat capacity close to 2. If, for example, a total dose
of 40 Mrad
needs to be delivered to biomass and it is done all at once, the AT is about
200 C.
Taking into account, for example, that the biomass prior to irradiation might
have a
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temperature around 25 C, the temperature could spike at about 225 C, wherein
the
material would be significantly decomposed. Alternatively, irradiating twice
with equal
20 Mrad doses and with cooling in between irradiations would cause a AT of
about 100
C. If the temperature of the biomass is already around 25 C , the material
could spike at
about 125 C, a much more reasonable temperature which, allowing for cooling,
would
probably not decompose the material to too high a degree.
[0027] After treatment in the first vault in the row (vaults 316, for
example in R1,
R2, R3, R4, R5, R6, R7, R8 and R9) in the first column of vaults (e.g., Cl),
each portion
of biomass is sent to the second vault (a second column, C2) in its row (e.g.,
R1-R9) for
further treatment. Between the treatments, for example, while biomass is being
conveyed
from Cl to C2, the biomass can be cooled. Thus, in the example shown in FIG.
3B,
biomass is sent from each of the first vaults 316 and Cl to the associated
second column,
C2, of vaults 318, e.g., utilizing a pneumatic system. In implementations in
which the
rows include more than two vaults, each biomass portion would then be sent to
one or
more subsequent vaults in its row.
[0028] After being treated in each of the vaults in the row (vaults 316
and 318 in the
illustrated example), the biomass is conveyed pneumatically through an outlet
324, to
tubes 326 which merge streams into a single tube 328. Tube 328 pneumatically
conveys
the treated biomass to bag elevator house 330. Elevator house 330 contains
equipment
similar to elevator house 306 (e.g., bag houses, conveyor and elevators). The
elevator
house accepts the biomass from tube 328 via an inlet and then can convey the
material to
storage silos 332. The elevator house can then send the treated biomass from
the storage
silos to further processing, distribution or other storage areas pneumatically
through tube
334.
[0029] In the embodiment shown as FIG. 3B, the flow path, as indicated
by the
arrows, shows each portion of biomass can be irradiated twice, for example
first in the
first column of vaults 316 followed by irradiation in the second column of
vaults 318.
The biomass can be conveyed under a scan horn that is, for example, 70" wide
and the
biomass can be in a layer that is, for example, about 0.25" thick. If the
biomass has a
density of about 34.5 lbs/ ft3 and the material is conveyed at a rate of 20
ft/min, about
4,740 lb/hr can be treated through vaults 316 and 318. Using the entire array
shown in
FIGS. 3A-C, such that nine portions of biomass are treated in the 9 rows of
vaults,
approximately 42,660 lb/hr of biomass can be treated. Optionally, more or
fewer vaults
can be utilized, increasing or decreasing the throughput for a set processing
rate. In

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addition, in some embodiments the average rate of processing a biomass is more
than
about 500 lb/hr per portion of biomass (e.g., more than about 10001b/hr, more
than about
15001b/hr, more than about 20001b/hr, more than about 25001b/hr, more than
about
30001b/hr, more than about 35001b/hr, more than about 40001b/hr, more than
about
45001b/hr, more than more than about 50001b/hr, more than about 60001b/hr, or
between
about 1000 and 5000 lb/hr). If the power of the irradiator is high enough even
higher
processing speeds can be achieved, for example, greater than about 15,000 lb
per hour,
greater than about 20,000 lb per hour, greater than about 25,000 lb per hour
or even up to
about 30,000 lb per hour. The material can be processed at lower rates as
well. The rates
of conveying the material under an electron beam can be optionally varied
greatly and
independently between the irradiators in various vaults. For example, the
conveying rate
can be slowed down to increase the irradiation dose or increased to decrease
the
irradiation dose under one of more of the irradiators.
[0030] The vaults that make up an array of treaters can include vaults
sharing one or
more common walls as shown in the detailed view FIG. 3C. For example, vault
318 and
vault 316 share the common wall 350. The vaults, for example 316 and 318 can
include
equipment and systems for treating a material such as a biomass.
[0031] The radiation dose applied in each of the vaults can be
approximately the
same. Alternatively, the radiation dose can be different in each of the
vaults. For
example, once an electron beam is brought to its optimal and/or target
voltage, the
radiation dose applied in each vault can be varied independently between about
1 Mrad
and about 200 Mrad (e.g., between 10 Mrad and about 150Mrad, between about 10
Mrad
and about 100 Mrad, between about 10 Mrad and about 50 Mrad, between about 1
and
about 50 Mrad). The irradiation dose in each vault can be less than about
50Mrad (e.g.,
less than about 45 Mrad, less than about 40 Mrad, less than about 35 Mrad,
less than
about 30 Mrad, less than about 25 Mrad, less than about 20 Mrad, less than
about 15
Mrad, less than about 10 Mrad). The irradiation dose in each value can
independently be
at least 1 Mrad (e.g., at least 2 Mrad, at least, 3 Mrad, at least 4 Mrad, at
least 5 Mrad, at
least 6 Mrad, at least 7 Mrad, at least 8 Mrad, at least 9 Mrad, at least 10
Mrad, at least
20 Mrad, at least 30 Mrad, at least 40 Mrad, at least 50 Mrad.
[0032] The vaults are designed to contain radiation as well as house the
irradiation
devices and associated equipment. Preferably the vaults are built with
radiation opaque
materials, for example concrete, lead, steel, soil or combinations of these. A
typical vault
material is concrete which has a halving-thickness (the thickness to reduce
the radiation
by half) of 2.4". Therefore, walls can be about 4 feet thick which would
reduce radiation
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striking the walls to 1/1,000,000th of the original strength. For a dose of
250 kGy applied
inside the structure, the resulting radiation outside the structure, assuming
an F-factor of
1.0, will be 0.00025 millirem, well below safe limits. Walls can be thinner or
thicker, for
example between 3 and 12 feet thick. In addition to walls, floors and
ceilings, the vaults
can have doors made of radiation opaque materials. The materials can be
layered, for
example, doors can be made as layers of 1" lead over 6" of steel over 1" of
lead.
[0033] Some more details and reiterations of processes for treating a
feedstock that
can be utilized, for example, with the embodiments already discussed above, or
in other
embodiments, are described in the following disclosures.
RADIATION TREATMENT
[0034] The feedstock can be treated with radiation to modify its
structure to reduce
its recalcitrance. Such treatment can, for example, reduce the average
molecular weight
of the feedstock, change the crystalline structure of the feedstock, and/or
increase the
surface area and/or porosity of the feedstock. Radiation can be by, for
example, electron
beam, ion beam, 100 nm to 280 nm ultraviolet (UV) light, gamma or X-ray
radiation.
Radiation treatments and systems for treatments are discussed in U.S. Patent
8,142,620
and U.S. Patent Application Serial No. 12/417, 731, the entire disclosures of
which are
incorporated herein by reference.
[0035] Each form of radiation ionizes the biomass via particular
interactions, as
determined by the energy of the radiation. Heavy charged particles primarily
ionize
matter via Coulomb scattering; furthermore, these interactions produce
energetic
electrons that may further ionize matter. Alpha particles are identical to the
nucleus of a
helium atom and are produced by the alpha decay of various radioactive nuclei,
such as
isotopes of bismuth, polonium, astatine, radon, francium, radium, several
actinides, such
as actinium, thorium, uranium, neptunium, curium, californium, americium, and
plutonium. Electrons interact via Coulomb scattering and bremsstrahlung
radiation
produced by changes in the velocity of electrons.
[0036] When particles are utilized, they can be neutral (uncharged),
positively
charged or negatively charged. When charged, the charged particles can bear a
single
positive or negative charge, or multiple charges, e.g., one, two, three or
even four or
more charges. In instances in which chain scission is desired to change the
molecular
structure of the carbohydrate containing material, positively charged
particles may be
desirable, in part, due to their acidic nature. When particles are utilized,
the particles can
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have the mass of a resting electron, or greater, e.g., 500, 1000, 1500, or
2000 or more
times the mass of a resting electron. For example, the particles can have a
mass of from
about 1 atomic unit to about 150 atomic units, e.g., from about 1 atomic unit
to about 50
atomic units, or from about 1 to about 25, e.g., 1, 2, 3, 4, 5, 10, 12 or 15
atomic units.
[0037] Gamma radiation has the advantage of a significant penetration
depth into a
variety of material in the sample.
[0038] In embodiments in which the irradiating is performed with
electromagnetic
radiation, the electromagnetic radiation can have, e.g., energy per photon (in
electron
volts) of greater than 102 eV, e.g., greater than 103, 104, 105, 106, or even
greater than 107
eV. In some embodiments, the electromagnetic radiation has energy per photon
of
between 104 and 107, e.g., between 105 and 106 eV. The electromagnetic
radiation can
have a frequency of, e.g., greater than 1016 Hz, greater than 1017 Hz, 1018,
1019, 1020, or
even greater than 1021 Hz. In some embodiments, the electromagnetic radiation
has a
frequency of between 1018 and 1022 Hz, e.g., between 1019 to 1021 Hz.
[0039] Electron bombardment may be performed using an electron beam
device that
has a nominal energy of less than 10 MeV, e.g., less than 7 MeV, less than 5
MeV, or
less than 2 MeV, e.g., from about 0.5 to 1.5 MeV, from about 0.8 to 1.8 MeV,
or from
about 0.7 to 1 MeV. In some implementations the nominal energy is about 500 to
800
keV.
[0040] The electron beam may have a relatively high total beam power
(the
combined beam power of all accelerating heads, or, if multiple accelerators
are used, of
all accelerators and all heads), e.g., at least 25 kW, e.g., at least 30, 40,
50, 60, 65, 70, 80,
100, 125, or 150 kW. In some cases, the power is even as high as 500 kW, 750
kW, or
even 1000 kW or more. In some cases the electron beam has a beam power of 1200
kW
or more, e.g., 1400, 1600, 1800, or even 3000 kW.
[0041] This high total beam power is usually achieved by utilizing
multiple
accelerating heads. For example, the electron beam device may include two,
four, or
more accelerating heads. The use of multiple heads, each of which has a
relatively low
beam power, prevents excessive temperature rise in the material, thereby
preventing
burning of the material, and also increases the uniformity of the dose through
the
thickness of the layer of material.
[0042] It is generally preferred that the bed of biomass material has a
relatively
uniform thickness. In some embodiments the thickness is less than about 1 inch
(e.g.,
less than about 0.75 inches, less than about 0.5 inches, less than about 0.25
inches, less
than about 0.1 inches, between about 0.1 and 1 inch, between about 0.2 and 0.3
inches).
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[0043] It is desirable to treat the material as quickly as possible. In
general, it is
preferred that treatment be performed at a dose rate of greater than about
0.25 Mrad per
second, e.g., greater than about 0.5, 0.75, 1, 1.5, 2, 5, 7, 10, 12, 15, or
even greater than
about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second. Higher dose
rates
allow a higher throughput for a target (e.g., the desired) dose. Higher dose
rates generally
require higher line speeds, to avoid thermal decomposition of the material. In
one
implementation, the accelerator is set for 3 MeV, 50 mA beam current, and the
line
speed is 24 feet/minute, for a sample thickness of about 20 mm (e.g.,
comminuted corn
cob material with a bulk density of 0.5 g/cm3).
[0044] In some embodiments, electron bombardment is performed until the
material
receives a total dose of at least 0.1 Mrad, 0.25 Mrad, 1 Mrad, 5 Mrad, e.g.,
at least 10,
20, 30 or at least 40 Mrad. In some embodiments, the treatment is performed
until the
material receives a dose of from about 10 Mrad to about 50 Mrad, e.g., from
about 20
Mrad to about 40 Mrad, or from about 25 Mrad to about 30 Mrad. In some
implementations, a total dose of 25 to 35 Mrad is preferred, applied ideally
over a couple
of passes, e.g., at 5 Mrad/pass with each pass being applied for about one
second.
Cooling methods, systems and equipment can be used before, during, after and
in
between radiations, for example, utilizing a cooling screw conveyor and/or a
cooled
vibratory conveyor.
[0045] Using multiple heads as discussed above, the material can be
treated in
multiple passes, for example, two passes at 10 to 20 Mrad/pass, e.g., 12 to 18
Mrad/pass,
separated by a few seconds of cool-down, or three passes of 7 to 12 Mrad/pass,
e.g., 5 to
20 Mrad/pass, 10 to 40 Mrad/pass, 9 to 11 Mrad/pass. As discussed herein,
treating the
material with several relatively low doses, rather than one high dose, tends
to prevent
overheating of the material and also increases dose uniformity through the
thickness of
the material. In some implementations, the material is stirred or otherwise
mixed during
or after each pass and then smoothed into a uniform layer again before the
next pass, to
further enhance treatment uniformity.
[0046] In some embodiments, electrons are accelerated to, for example, a
speed of
greater than 75 percent of the speed of light, e.g., greater than 85, 90, 95,
or 99 percent of
the speed of light.
[0047] In some embodiments, any processing described herein occurs on
lignocellulosic material that remains dry as acquired or that has been dried,
e.g., using
heat and/or reduced pressure. For example, in some embodiments, the cellulosic
and/or
lignocellulosic material has less than about 25 wt. % retained water, measured
at 25 C
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and at fifty percent relative humidity (e.g., less than about 20 wt.%, less
than about 15
wt.%, less than about 14 wt.%, less than about 13 wt.%, less than about 12
wt.%, less
than about 10 wt.%, less than about 9 wt.%, less than about 8 wt.%, less than
about 7
wt.%, less than about 6 wt.%, less than about 5 wt.%, less than about 4 wt.%,
less than
about 3 wt.%, less than about 2 wt.%, less than about 1 wt.%, or less than
about 0.5
wt.%.
[0048] In some embodiments, two or more ionizing sources can be used,
such as two
or more electron sources. For example, samples can be treated, in any order,
with a
beam of electrons, followed by gamma radiation and UV light having wavelengths
from
about 100 nm to about 280 nm. In some embodiments, samples are treated with
three
ionizing radiation sources, such as a beam of electrons, gamma radiation, and
energetic
UV light. The biomass is conveyed through the treatment zone where it can be
bombarded with electrons.
[0049] It may be advantageous to repeat the treatment to more thoroughly
reduce the
recalcitrance of the biomass and/or further modify the biomass. In particular
the process
parameters can be adjusted after a first (e.g., second, third, fourth or more)
pass
depending on the recalcitrance of the material. In some embodiments, a
conveyor can be
used which includes a circular system where the biomass is conveyed multiple
times
through the various processes described above. In some other embodiments,
multiple
treatment devices (e.g., electron beam generators) are used to treat the
biomass multiple
(e.g., 2, 3, 4 or more) times. In yet other embodiments, a single electron
beam generator
may be the source of multiple beams (e.g., 2, 3, 4 or more beams) that can be
used for
treatment of the biomass.
[0050] The effectiveness in changing the molecular/supermolecular
structure and/or
reducing the recalcitrance of the carbohydrate-containing biomass depends on
the
electron energy used and the dose applied, while exposure time depends on the
power
and dose. In some embodiments, the dose rate and total dose are adjusted so as
not to
destroy (e.g., char or burn) the biomass material. For example, the
carbohydrates should
not be damaged in the processing so that they can be released from the biomass
intact,
e.g. as monomeric sugars.
[0051] In some embodiments, the treatment (with any electron source or a
combination of sources) is performed until the material receives a dose of at
least about
0.05 Mrad, e.g., at least about 0.1, 0.25, 0.5, 0.75, 1.0, 2.5, 5.0, 7.5,
10.0, 15, 20, 25, 30,
40, 50, 60, 70, 80, 90, 100, 125, 150, 175, or 200 Mrad. In some embodiments,
the
treatment is performed until the material receives a dose of between 0.1-100
Mrad, 1-

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200, 5-200, 10-200, 5-150, 50-150 Mrad, 5-100, 5-50, 5-40, 10-50, 10-75, 15-
50, 20-35
Mrad.
[0052] In some embodiments, relatively low doses of radiation are
utilized, e.g., to
increase the molecular weight of a cellulosic or lignocellulosic material
(with any
radiation source or a combination of sources described herein). For example, a
dose of at
least about 0.05 Mrad, e.g., at least about 0.1 Mrad or at least about 0.25,
0.5, 0.75. 1.0,
1.5, 2.0, 2.5, 3.0, 3.5, 4.0, or at least about 5.0 Mrad. In some embodiments,
the
irradiation is performed until the material receives a dose of between 0.1Mrad
and 2.0
Mrad, e.g., between 0.5 Mrad and 4.0 Mrad or between 1.0 Mrad and 3.0 Mrad.
It also can be desirable to irradiate from multiple directions, simultaneously
or
sequentially, in order to achieve a desired degree of penetration of radiation
into the
material. For example, depending on the density and moisture content of the
material,
such as wood, and the type of radiation source used (e.g., gamma or electron
beam), the
maximum penetration of radiation into the material may be only about 0.75
inch. In such
cases, a thicker section (up to 1.5 inch) can be irradiated by first
irradiating the material
from one side, and then turning the material over and irradiating from the
other side.
Irradiation from multiple directions can be particularly useful with electron
beam
radiation, which irradiates faster than gamma radiation but typically does not
achieve as
great a penetration depth.
RADIATION OPAQUE MATERIALS
[0053] As previously discussed, the invention can include processing the
material in
a vault and/or bunker that is constructed using radiation opaque materials. In
some
implementations, the radiation opaque materials are selected to be capable of
shielding
the components from X-rays with high energy (short wavelength), which can
penetrate
many materials. One important factor in designing a radiation shielding
enclosure is the
attenuation length of the materials used, which will determine the required
thickness for
a particular material, blend of materials, or layered structure. The
attenuation length is
the penetration distance at which the radiation is reduced to approximately
1/e (e =
Euler's number) times that of the incident radiation. Although virtually all
materials are
radiation opaque if thick enough, materials containing a high compositional
percentage
(e.g., density) of elements that have a high Z value (atomic number) have a
shorter
radiation attenuation length and thus if such materials are used a thinner,
lighter
shielding can be provided. Examples of high Z value materials that are used in
radiation
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shielding are tantalum and lead. Another important parameter in radiation
shielding is
the halving distance, which is the thickness of a particular material that
will reduce
gamma ray intensity by 50%. As an example for X-ray radiation with an energy
of 0.1
MeV the halving thickness is about 15.1 mm for concrete and about 2.7 mm for
lead,
while with an X-ray energy of 1 MeV the halving thickness for concrete is
about 44.45
mm and for lead is about 7.9 mm. Radiation opaque materials can be materials
that are
thick or thin so long as they can reduce the radiation that passes through to
the other side.
Thus, if it is desired that a particular enclosure have a low wall thickness,
e.g., for light
weight or due to size constraints, the material chosen should have a
sufficient Z value
and/or attenuation length so that its halving length is less than or equal to
the desired
wall thickness of the enclosure.
[0054] In some cases, the radiation opaque material may be a layered
material, for
example having a layer of a higher Z value material, to provide good
shielding, and a
layer of a lower Z value material to provide other properties (e.g.,
structural integrity,
impact resistance, etc.). In some cases, the layered material may be a "graded-
T'
laminate, e.g., including a laminate in which the layers provide a gradient
from high-Z
through successively lower-Z elements. In some cases the radiation opaque
materials can
be interlocking blocks, for example, lead and/or concrete blocks can be
supplied by
NELCO Worldwide (Burlington, MA), and reconfigurable vaults can be utilized.
[0055] A radiation opaque material can reduce the radiation passing
through a
structure (e.g., a wall, door, ceiling, enclosure, a series of these or
combinations of these)
formed of the material by about at least about 10 %, (e.g., at least about
20%, at least
about 30%, at least about 40%, at least about 50%, at least about 60%, at
least about
70%, at least about 80%, at least about 90%, at least about 95%, at least
about 96%, at
least about 97%, at least about 98%, at least about 99%, at least about 99.9%,
at least
about 99.99%, at least about 99.999%) as compared to the incident radiation.
Therefore,
an enclosure made of a radiation opaque material can reduce the exposure of
equipment/system/components by the same amount. Radiation opaque materials can
include stainless steel, metals with Z values above 25 (e.g., lead, iron),
concrete, dirt,
sand and combinations thereof. Radiation opaque materials can include a
barrier in the
direction of the incident radiation of at least about lmm (e.g., 5 mm, lOmm, 5
cm, 10
cm, 100cm, lm and even at least about 10m).
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RADIATION SOURCES
[0056] The type of radiation determines the kinds of radiation sources
used as well as
the radiation devices and associated equipment. The methods, systems and
equipment
described herein, for example, for treating materials with radiation, can
utilized sources
as described herein as well as any other useful source.
[0057] Sources of gamma rays include radioactive nuclei, such as
isotopes of cobalt,
calcium, technetium, chromium, gallium, indium, iodine, iron, krypton,
samarium,
selenium, sodium, thallium, and xenon.
[0058] Sources of X-rays include electron beam collision with metal
targets, such as
tungsten or molybdenum or alloys, or compact light sources, such as those
produced
commercially by Lyncean.
[0059] Alpha particles are identical to the nucleus of a helium atom and
are produced
by the alpha decay of various radioactive nuclei, such as isotopes of bismuth,
polonium,
astatine, radon, francium, radium, several actinides, such as actinium,
thorium, uranium,
neptunium, curium, californium, americium, and plutonium.
[0060] Sources for ultraviolet radiation include deuterium or cadmium
lamps.
[0061] Sources for infrared radiation include sapphire, zinc, or
selenide window
ceramic lamps.
[0062] Sources for microwaves include klystrons, Slevin type RF sources,
or atom
beam sources that employ hydrogen, oxygen, or nitrogen gases.
[0063] Accelerators used to accelerate the particles (e.g., electrons or
ions) can be
DC (e.g., electrostatic DC or electrodynamic DC), RF linear, magnetic
induction linear
or continuous wave. For example, various irradiating devices may be used in
the
methods disclosed herein, including field ionization sources, electrostatic
ion separators,
field ionization generators, thermionic emission sources, microwave discharge
ion
sources, recirculating or static accelerators, dynamic linear accelerators,
van de Graaff
accelerators, Cockroft Walton accelerators (e.g., PELLETRON accelerators),
LINACS,
Dynamitrons (e.g., DYNAMITRON accelerators), cyclotrons, synchrotrons,
betatrons,
transformer-type accelerators, microtrons, plasma generators, cascade
accelerators, and
folded tandem accelerators. For example, cyclotron type accelerators are
available from
IBA, Belgium, such as the RHODOTRONTm system, while DC type accelerators are
available from RDI, now IBA Industrial, such as the DYNAMITRON . Other
suitable
accelerator systems include, for example: DC insulated core transformer (ICT)
type
systems, available from Nissin High Voltage, Japan; S-band LINACs, available
from L3-
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PSD (USA), Linac Systems (France), Mevex (Canada), and Mitsubishi Heavy
Industries
(Japan); L-band LINACs, available from Iotron Industries (Canada); and ILU-
based
accelerators, available from Budker Laboratories (Russia). Ions and ion
accelerators are
discussed in Introductory Nuclear Physics, Kenneth S. Krane, John Wiley &
Sons, Inc.
(1988), Krsto Prelee, FIZIKA B 6 (1997) 4, 177-206, Chu, William T., "Overview
of
Light-Ion Beam Therapy", Columbus-Ohio, ICRU-IAEA Meeting, 18-20 March 2006,
Iwata, Y. et al., "Alternating-Phase-Focused IH-DTL for Heavy-Ion Medical
Accelerators", Proceedings of EPAC 2006, Edinburgh, Scotlandõ and Leitner,
C.M. et
al., "Status of the Superconducting ECR Ion Source Venus", Proceedings of EPAC
2000,
Vienna, Austria. Some particle accelerators and their uses are disclosed, for
example, in
U.S. Pat. No. 7,931,784 to Medoff, the complete disclosure of which is
incorporated
herein by reference.
[0064] Electrons may be produced by radioactive nuclei that undergo beta
decay,
such as isotopes of iodine, cesium, technetium, and iridium. Alternatively, an
electron
gun can be used as an electron source via thermionic emission and accelerated
through
an accelerating potential. An electron gun generates electrons, which are then
accelerated through a large potential (e.g., greater than about 500 thousand,
greater than
about lmillion, greater than about 2 million, greater than about 5 million,
greater than
about 6 million, greater than about 7 million, greater than about 8 million,
greater than
about 9 million, or even greater than 10 million volts) and then scanned
magnetically in
the x-y plane, where the electrons are initially accelerated in the z
direction down the
accelerator tube and extracted through a foil window. Scanning the electron
beams is
useful for increasing the irradiation surface when irradiating materials,
e.g., a biomass,
that is conveyed through the scanned beam. Scanning the electron beam also
distributes
the thermal load homogenously on the window and helps reduce the foil window
rupture
due to local heating by the electron beam. Window foil rupture is a cause of
significant
down-time due to subsequent necessary repairs and re-starting the electron
gun.
[0065] Various other irradiating devices may be used in the methods
disclosed
herein, including field ionization sources, electrostatic ion separators,
field ionization
generators, thermionic emission sources, microwave discharge ion sources,
recirculating
or static accelerators, dynamic linear accelerators, van de Graaff
accelerators, and folded
tandem accelerators. Such devices are disclosed, for example, in U.S. Pat. No.
7,931,784
to Medoff, the complete disclosure of which is incorporated herein by
reference.
[0066] A beam of electrons can be used as the radiation source. A beam
of electrons
has the advantages of high dose rates (e.g., 1, 5, or even 10 Mrad per
second), high
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throughput, less containment, and less confinement equipment. Electron beams
can also
have high electrical efficiency (e.g., 80%), allowing for lower energy usage
relative to
other radiation methods, which can translate into a lower cost of operation
and lower
greenhouse gas emissions corresponding to the smaller amount of energy used.
Electron
beams can be generated, e.g., by electrostatic generators, cascade generators,
transformer
generators, low energy accelerators with a scanning system, low energy
accelerators with
a linear cathode, linear accelerators, and pulsed accelerators.
[0067] Electrons can also be more efficient at causing changes in the
molecular
structure of carbohydrate-containing materials, for example, by the mechanism
of chain
scission. In addition, electrons having energies of 0.5-10 MeV can penetrate
low density
materials, such as the biomass materials described herein, e.g., materials
having a bulk
density of less than 0.5 &in', and a depth of 0.3-10 cm. Electrons as an
ionizing
radiation source can be useful, e.g., for relatively thin piles, layers or
beds of materials,
e.g., less than about 0.5 inch, e.g., less than about 0.4 inch, 0.3 inch, 0.25
inch, or less
than about 0.1 inch. In some embodiments, the energy of each electron of the
electron
beam is from about 0.3 MeV to about 2.0 MeV (million electron volts), e.g.,
from about
0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV. Methods of
irradiating materials are discussed in U.S. Pat. App. Pub. 2012/0100577 Al,
filed
October 18, 2011, the entire disclosure of which is herein incorporated by
reference.
[0068] Electron beam irradiation devices may be procured commercially or
built. For
example, elements or components such inductors, capacitors, casings, power
sources,
cables, wiring, voltage control systems, current control elements, insulating
material,
microcontrollers and cooling equipment can be purchased and assembled into a
device.
Optionally, a commercial device can be modified and/or adapted. For example,
devices
and components can be purchased from any of the commercial sources described
herein
including Ion Beam Applications (Louvain-la-Neuve, Belgium), Wasik Associates
Inc.
(Dracut, MA), NHV Corporation (Japan), the Titan Corporation (San Diego, CA),
Vivirad High Voltage Corp (Billerica, MA) and/or Budker Laboratories (Russia).
Typical electron energies can be 0.5 MeV, 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or
10
MeV. Typical electron beam irradiation device power can be 1 kW, 5 kW, 10 kW,
20
kW, 50 kW, 60 kW, 70 kW, 80 kW, 90 kW, 100 kW, 125 kW, 150 kW, 175 kW, 200
kW, 250 kW, 300 kW, 350 kW, 400 kW, 450 kW, 500 kW, 600 kW, 700 kW, 800 kW,
900 kW or even 1000 kW. Accelerators that can be used include NHV irradiators
medium energy series EPS-500 (e.g., 500 kV accelerator voltage and 65, 100 or
150 mA
beam current), EPS-800 (e.g., 800 kV accelerator voltage and 65 or 100 mA beam

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current), or EPS-1000 (e.g., 1000 kV accelerator voltage and 65 or 100 mA beam
current). Also, accelerators from NHV's high energy series can be used such as
EPS-
1500 (e.g., 1500 kV accelerator voltage and 65 mA beam current), EPS-2000
(e.g., 2000
kV accelerator voltage and 50 mA beam current), EPS-3000 (e.g., 3000 kV
accelerator
voltage and 50 mA beam current) and EPS-5000 (e.g., 5000 and 30 mA beam
current).
[0069] Tradeoffs in considering electron beam irradiation device power
specifications include cost to operate, capital costs, depreciation, and
device footprint.
Tradeoffs in considering exposure dose levels of electron beam irradiation
would be
energy costs and environment, safety, and health (ESH) concerns. Typically,
generators
are housed in a vault, e.g., of lead or concrete, especially for production
from X-rays that
are generated in the process. Tradeoffs in considering electron energies
include energy
costs.
[0070] The electron beam irradiation device can produce either a fixed
beam or a
scanning beam. A scanning beam may be advantageous with large scan sweep
length
and high scan speeds, as this would effectively replace a large, fixed beam
width.
Further, available sweep widths of 0.5 m, 1 m, 2 m or more are available. The
scanning
beam is preferred in most embodiments described herein because of the larger
scan width
and reduced possibility of local heating and failure of the windows.
ELECTRON GUNS ¨ WINDOWS
[0071] The extraction system for an electron accelerator can include two
window
foils. The cooling gas in the two foil window extraction system can be a purge
gas or a
mixture, for example air, or a pure gas. In one embodiment the gas is an inert
gas such
as nitrogen, argon, helium and or carbon dioxide. It is preferred to use a gas
rather than a
liquid since energy losses to the electron beam are minimized. Mixtures of
pure gas can
also be used, either pre-mixed or mixed in line prior to impinging on the
windows or in
the space between the windows. The cooling gas can be cooled, for example, by
using a
heat exchange system (e.g., a chiller) and/or by using boil off from a
condensed gas (e.g.,
liquid nitrogen, liquid helium). Window foils are described in
PCT/US2013/64332 filed
October 10, 2013 the full disclosure of which is incorporated by reference
herein.
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HEATING AND THROUGHPUT DURING RADIATION TREATMENT
[0072] Several processes can occur in biomass when electrons from an
electron beam
interact with matter in inelastic collisions. For example, ionization of the
material, chain
scission of polymers in the material, cross linking of polymers in the
material, oxidation
of the material, generation of X-rays ("Bremsstrahlung") and vibrational
excitation of
molecules (e.g., phonon generation). Without being bound to a particular
mechanism, the
reduction in recalcitrance can be due to several of these inelastic collision
effects, for
example ionization, chain scission of polymers, oxidation and phonon
generation. Some
of the effects (e.g., especially X-ray generation), necessitate shielding and
engineering
barriers, for example, enclosing the irradiation processes in a concrete (or
other radiation
opaque material) vault. Another effect of irradiation, vibrational excitation,
is equivalent
to heating up the sample. Heating the sample by irradiation can help in
recalcitrance
reduction, but excessive heating can destroy the material, as will be
explained below.
[0073] The adiabatic temperature rise (AT) from adsorption of ionizing
radiation is
given by the equation: AT = D/Cp : where D is the average dose in kGy, Cp is
the heat
capacity in J/g C, and AT is the change in temperature in C. A typical dry
biomass
material will have a heat capacity close to 2. Wet biomass will have a higher
heat
capacity dependent on the amount of water since the heat capacity of water is
very high
(4.19 J/g C). Metals have much lower heat capacities, for example 304
stainless steel
has a heat capacity of 0.5 J/g C. The temperature change due to the instant
adsorption of
radiation in a biomass and stainless steel for various doses of radiation is
shown in Table
1. At the higher temperatures biomass will decompose causing extreme deviation
from
the estimated changes in temperature.
Table 1: Calculated Temperature increase for biomass and stainless steel.
Dose (Mrad) Estimated Biomass AT ( C) Steel AT ( C)
50 200
50 250 (Decomposed) 1000
100 500 (Decomposed) 2000
150 750 (Decomposed) 3000
200 1000 (Decomposed) 4000
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[0074] High temperatures can destroy and or modify the biopolymers in
biomass so
that the polymers (e.g., cellulose) are unsuitable for further processing. A
biomass
subjected to high temperatures can become dark, sticky and give off odors
indicating
decomposition. The stickiness can even make the material hard to convey. The
odors can
be unpleasant and be a safety issue. In fact, keeping the biomass below about
200 C has
been found to be beneficial in the processes described herein (e.g., below
about 190 C,
below about 180 C, below about 170 C, below about 160 C, below about 150 C,
below
about 140 C, below about 130 C, below about 120 C, below about 110 C, between
about 60 C and 180 C, between about 60 C and 160 C, between about 60 C and 150
C,
between about 60 C and 140 C, between about 60 C and 130 C, between about 60 C
and 120 C, between about 80 C and 180 C, between about 100 C and 180 C,
between
about 120 C and 180 C, between about 140 C and 180 C, between about 160 C and
180 C, between about 100 C and 140 C, between about 80 C and 120 C).
[0075] It has been found that irradiation above about 10 Mrad is
desirable for the
processes described herein (e.g., reduction of recalcitrance). A high
throughput is also
desirable so that the irradiation does not become a bottle neck in processing
the biomass.
The treatment is governed by a Dose rate equation: M = FP/D=time, where M is
the mass
of irradiated material (kg), F is the fraction of power that is adsorbed (unit
less), P is the
emitted power (kW=Voltage in MeV x Current in mA), time is the treatment time
(sec)
and D is the adsorbed dose (kGy). In an exemplary process where the fraction
of
adsorbed power is fixed, the Power emitted is constant and a set dosage is
desired, the
throughput (e.g., M, the biomass processed) can be increased by increasing the
irradiation time. However, increasing the irradiation time without allowing
the material
to cool, can excessively heat the material as exemplified by the calculations
shown
above. Since biomass has a low thermal conductivity (less than about 0.1 Wm-1K-
1), heat
dissipation is slow, unlike, for example metals (greater than about 10 Wm-
11(4) which
can dissipate energy quickly as long as there is a heat sink to transfer the
energy to.
ELECTRON GUNS ¨ BEAM STOPS
[0076] In some embodiments the systems and methods include a beam stop
(e.g., a
shutter). For example, the beam stop can be used to quickly stop or reduce the
irradiation of material without powering down the electron beam device.
Alternatively
the beam stop can be used while powering up the electron beam, e.g., the beam
stop can
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stop the electron beam until a beam current of a desired level is achieved.
The beam stop
can be placed between the primary foil window and a secondary foil window. For
example, the beam stop can be mounted so that it is movable, that is, so that
it can be
moved into and out of the beam path. Even partial coverage of the beam can be
used, for
example, to control the dose of irradiation. The beam stop can be mounted to
the floor,
to a conveyor for the biomass, to a wall, to the radiation device (e.g., at
the scan horn), or
to any structural support. Preferably the beam stop is fixed in relation to
the scan horn so
that the beam can be effectively controlled by the beam stop. The beam stop
can
incorporate a hinge, a rail, wheels, slots, or other means allowing for its
operation in
moving into and out of the beam. The beam stop can be made of any material
that will
stop at least 5% of the electrons, e.g., at least 10%, 20%, 30%, 40%, 50%,
60%, 70%, at
least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or even about
100% of the electrons.
[0077] The beam stop can be made of a metal including, but not limited
to, stainless
steel, lead, iron, molybdenum, silver, gold, titanium, aluminum, tin, or
alloys of these, or
laminates (layered materials) made with such metals (e.g., metal-coated
ceramic, metal-
coated polymer, metal-coated composite, multilayered metal materials).
[0078] The beam stop can be cooled, for example, with a cooling fluid
such as an
aqueous solution or a gas. The beam stop can be partially or completely
hollow, for
example with cavities. Interior spaces of the beam stop can be used for
cooling fluids
and gases. The beam stop can be of any shape, including flat, curved, round,
oval,
square, rectangular, beveled and wedged shapes.
[0079] The beam stop can have perforations so as to allow some electrons
through,
thus controlling (e.g., reducing) the levels of radiation across the whole
area of the
window, or in specific regions of the window. The beam stop can be a mesh
formed, for
example, from fibers or wires. Multiple beam stops can be used, together or
independently, to control the irradiation. The beam stop can be remotely
controlled, e.g.,
by radio signal or hard wired to a motor for moving the beam into or out of
position.
BEAM DUMPS
[0080] The embodiments disclosed herein can also include a beam dump
when
utilizing a radiation treatment. A beam dump's purpose is to safely absorb a
beam of
charged particles. Like a beam stop, a beam dump can be used to block the beam
of
charged particles. However, a beam dump is much more robust than a beam stop,
and is
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intended to block the full power of the electron beam for an extended period
of time.
They are often used to block the beam as the accelerator is powering up.
[0081] Beam dumps are also designed to accommodate the heat generated by
such
beams, and are usually made from materials such as copper, aluminum, carbon,
beryllium, tungsten, or mercury. Beam dumps can be cooled, for example, using
a
cooling fluid that can be in thermal contact with the beam dump.
BIOMASS MATERIALS
[0082] Lignocellulosic materials include, but are not limited to, wood,
particle board,
forestry wastes (e.g., sawdust, aspen wood, wood chips), grasses, (e.g.,
switchgrass,
miscanthus, cord grass, reed canary grass), grain residues, (e.g., rice hulls,
oat hulls,
wheat chaff, barley hulls), agricultural waste (e.g., silage, canola straw,
wheat straw,
barley straw, oat straw, rice straw, jute, hemp, flax, bamboo, sisal, abaca,
corn cobs, corn
stover, soybean stover, corn fiber, alfalfa, hay, coconut hair), sugar
processing residues
(e.g., bagasse, beet pulp, agave bagasse), algae, seaweed, manure, sewage, and
mixtures
of any of these.
[0083] In some cases, the lignocellulosic material includes corncobs.
Ground or
hammermilled corncobs can be spread in a layer of relatively uniform thickness
for
irradiation, and after irradiation are easy to disperse in the medium for
further
processing. To facilitate harvest and collection, in some cases the entire
corn plant is
used, including the corn stalk, corn kernels, and in some cases even the root
system of
the plant.
[0084] Advantageously, no additional nutrients (other than a nitrogen
source, e.g.,
urea or ammonia) are required during fermentation of corncobs or cellulosic or
lignocellulosic materials containing significant amounts of corncobs.
[0085] Corncobs, before and after comminution, are also easier to convey
and
disperse, and have a lesser tendency to form explosive mixtures in air than
other
cellulosic or lignocellulosic materials such as hay and grasses.
[0086] Cellulosic materials include, for example, paper, paper products,
paper waste,
paper pulp, pigmented papers, loaded papers, coated papers, filled papers,
magazines,
printed matter (e.g., books, catalogs, manuals, labels, calendars, greeting
cards,
brochures, prospectuses, newsprint), printer paper, polycoated paper, card
stock,
cardboard, paperboard, materials having a high a-cellulose content such as
cotton, and
mixtures of any of these. For example paper products as described in U.S. App.
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13/396,365 ("Magazine Feedstocks" by Medoff et al., filed February 14, 2012),
the full
disclosure of which is incorporated herein by reference.
[0087] Cellulosic materials can also include lignocellulosic materials
which have
been partially or fully de-lignified.
[0088] In some instances other biomass materials can be utilized, for
example
starchy materials. Starchy materials include starch itself, e.g., corn starch,
wheat starch,
potato starch or rice starch, a derivative of starch, or a material that
includes starch, such
as an edible food product or a crop. For example, the starchy material can be
arracacha,
buckwheat, banana, barley, cassava, kudzu, ocra, sago, sorghum, regular
household
potatoes, sweet potato, taro, yams, or one or more beans, such as favas,
lentils or peas.
Blends of any two or more starchy materials are also starchy materials.
Mixtures of
starchy, cellulosic and or lignocellulosic materials can also be used. For
example, a
biomass can be an entire plant, a part of a plant or different parts of a
plant, e.g., a wheat
plant, cotton plant, a corn plant, rice plant or a tree. The starchy materials
can be treated
by any of the methods described herein.
[0089] Microbial materials that can be used as feedstock can include,
but are not
limited to, any naturally occurring or genetically modified microorganism or
organism
that contains or is capable of providing a source of carbohydrates (e.g.,
cellulose), for
example, protists, e.g., animal protists (e.g., protozoa such as flagellates,
amoeboids,
ciliates, and sporozoa) and plant protists (e.g., algae such alveolates,
chlorarachniophytes, cryptomonads, euglenids, glaucophytes, haptophytes, red
algae,
stramenopiles, and viridaeplantae). Other examples include seaweed, plankton
(e.g.,
macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and
femptoplankton), phytoplankton, bacteria (e.g., gram positive bacteria, gram
negative
bacteria, and extremophiles), yeast and/or mixtures of these. In some
instances,
microbial biomass can be obtained from natural sources, e.g., the ocean,
lakes, bodies of
water, e.g., salt water or fresh water, or on land. Alternatively or in
addition, microbial
biomass can be obtained from culture systems, e.g., large scale dry and wet
culture and
fermentation systems.
[0090] In other embodiments, the biomass materials, such as cellulosic,
starchy and
lignocellulosic feedstock materials, can be obtained from transgenic
microorganisms and
plants that have been modified with respect to a wild type variety. Such
modifications
may be, for example, through the iterative steps of selection and breeding to
obtain
desired traits in a plant. Furthermore, the plants can have had genetic
material removed,
modified, silenced and/or added with respect to the wild type variety. For
example,
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genetically modified plants can be produced by recombinant DNA methods, where
genetic modifications include introducing or modifying specific genes from
parental
varieties, or, for example, by using transgenic breeding wherein a specific
gene or genes
are introduced to a plant from a different species of plant and/or bacteria.
Another way
to create genetic variation is through mutation breeding wherein new alleles
are
artificially created from endogenous genes. The artificial genes can be
created by a
variety of ways including treating the plant or seeds with, for example,
chemical
mutagens (e.g., using alkylating agents, epoxides, alkaloids, peroxides,
formaldehyde),
irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alpha
particles, protons,
deuterons, UV radiation) and temperature shocking or other external stressing
and
subsequent selection techniques. Other methods of providing modified genes is
through
error prone PCR and DNA shuffling followed by insertion of the desired
modified DNA
into the desired plant or seed. Methods of introducing the desired genetic
variation in the
seed or plant include, for example, the use of a bacterial carrier,
biolistics, calcium
phosphate precipitation, electroporation, gene splicing, gene silencing,
lipofection,
microinjection and viral carriers. Additional genetically modified materials
have been
described in U.S. Application Serial No 13/396,369 filed February 14, 2012 the
full
disclosure of which is incorporated herein by reference.
[0091] Any of
the methods described herein can be practiced with mixtures of any
biomass materials described herein.
OTHER MATERIALS
[0092] Other
materials (e.g., natural or synthetic materials), for example, polymers,
can be treated and/or made utilizing the methods, equipment and systems
described
hererin.yor example polyethylene (e.g., linear low density ethylene and high
density
polyethylene), polystyrenes, sulfonated polystyrenes, poly (vinyl chloride),
polyesters
(e.g., nylons, DACRONTM, KODELTm), polyalkylene esters, poly vinyl esters,
polyamides (e.g., KEVLARTm), polyethylene terephthalate, cellulose acetate,
acetal,
poly acrylonitrile, polycarbonates (e.g., LEXANTm), acrylics [e.g., poly
(methyl
methacrylate), poly(methyl methacrylate), polyacrylonitrile], Poly urethanes,
polypropylene, poly butadiene, polyisobutylene, polyacrylonitrile,
polychloroprene (e.g.
neoprene), poly(cis-1,4-isoprene) [e.g., natural rubber], poly(trans-1,4-
isoprene) [e.g.,
gutta percha], phenol formaldehyde, melamine formaldehyde, epoxides,
polyesters, poly
amines, polycarboxylic acids, polylactic acids, polyvinyl alcohols,
polyanhydrides, poly
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fluoro carbons (e.g., TEFLONTm), silicons (e.g., silicone rubber),
polysilanes, poly ethers
(e.g., polyethylene oxide, polypropylene oxide), waxes, oils and mixtures of
these. Also
included are plastics, rubbers, elastomers, fibers, waxes, gels, oils,
adhesives,
thermoplastics, thermosets, biodegradable polymers, resins made with these
polymers,
other polymers, other materials and combinations thereof. The polymers can be
made by
any useful method including cationic polymerization, anionic polymerization,
radical
polymerization, metathesis polymerization, ring opening polymerization, graft
polymerization, addition polymerization. In some cases the treatments
disclosed herein
can be used, for example, for radically initiated graft polymerization and
cross linking.
Composites of polymers, for example, with glass, metals, biomass (e.g.,
fibers, particles),
ceramics can also be treated and/or made.
[0093] Other materials that can be treated by using the methods, systems
and
equipment disclosed herein are ceramic materials, minerals, metals, inorganic
compounds. For example, silicon and germanium crystals, silicon nitrides,
metal oxides,
semiconductors, insulators, cements and or conductors.
[0094] In addition, manufactured multipart or shaped materials (e.g.,
molded,
extruded, welded, riveted, layered or combined in any way) can be treated, for
example
cables, pipes, boards, enclosures, integrated semiconductor chips, circuit
boards, wires,
tires, windows, laminated materials, gears, belts, machines, combinations of
these. For
example, treating a material by the methods described herein can modify the
surfaces, for
example, making them susceptible to further functionalization, combinations
(e.g.,
welding) and/or treatment can cross link the materials.
BIOMASS MATERIAL PREPARATION ¨ MECHANICAL TREATMENTS
[0095] The biomass can be in a dry form, for example with less than
about 35%
moisture content (e.g., less than about 20 %, less than about 15 %, less than
about 10 %
less than about 5 %, less than about 4%, less than about 3 %, less than about
2 % or
even less than about 1 %). The biomass can also be delivered in a wet state,
for example
as a wet solid, a slurry or a suspension with at least about 10 wt% solids
(e.g., at least
about 20 wt.%, at least about 30 wt. %, at least about 40 wt.%, at least about
50 wt.%, at
least about 60 wt.%, at least about 70 wt.%).
[0096] The processes disclosed herein can utilize low bulk density
materials, for
example cellulosic or lignocellulosic feedstocks that have been physically
pretreated to
have a bulk density of less than about 0.75 g/cm3, e.g., less than about 0.7,
0.65, 0.60,
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0.50, 0.35, 0.25, 0.20, 0.15, 0.10, 0.05 or less, e.g., less than about 0.025
g/cm3. Bulk
density is determined using ASTM D1895B. Briefly, the method involves filling
a
measuring cylinder of known volume with a sample and obtaining a weight of the
sample. The bulk density is calculated by dividing the weight of the sample in
grams by
the known volume of the cylinder in cubic centimeters. If desired, low bulk
density
materials can be densified, for example, by methods described in U.S. Pat. No.
7,971,809
to Medoff, the full disclosure of which is hereby incorporated by reference.
[0097] In some cases, the pre-treatment processing includes screening of
the biomass
material. Screening can be through a mesh or perforated plate with a desired
opening
size, for example, less than about 6.35 mm (1/4 inch, 0.25 inch), (e.g., less
than about
3.18 mm (1/8 inch, 0.125 inch), less than about 1.59 mm (1/16 inch, 0.0625
inch), is less
than about 0.79 mm (1/32 inch, 0.03125 inch), e.g., less than about 0.51 mm
(1/50 inch,
0.02000 inch), less than about 0.40 mm (1/64 inch, 0.015625 inch), less than
about 0.23
mm (0.009 inch), less than about 0.20 mm (1/128 inch, 0.0078125 inch), less
than about
0.18 mm (0.007 inch), less than about 0.13 mm (0.005 inch), or even less than
about 0.10
mm (1/256 inch, 0.00390625 inch)). In one configuration the desired biomass
falls
through the perforations or screen and thus biomass larger than the
perforations or screen
are not irradiated. These larger materials can be re-processed, for example,
by
comminuting, or they can simply be removed from processing. In another
configuration
material that is larger than the perforations is irradiated and the smaller
material is
removed by the screening process or recycled. In this kind of a configuration,
the
conveyor itself (for example, a part of the conveyor) can be perforated or
made with a
mesh. For example, in one particular embodiment the biomass material may be
wet and
the perforations or mesh allow water to drain away from the biomass before
irradiation.
[0098] Screening of material can also be by a manual method, for
example, by an
operator or mechanoid (e.g., a robot equipped with a color, reflectivity or
other sensor)
that removes unwanted material. Screening can also be by magnetic screening
wherein a
magnet is disposed near the conveyed material and the magnetic material is
removed
magnetically.
[0099] Optional pre-treatment processing can include heating the
material. For
example, a portion of a conveyor conveying the biomass or other material can
be sent
through a heated zone. The heated zone can be created, for example, by IR
radiation,
microwaves, combustion (e.g., gas, coal, oil, biomass), resistive heating
and/or inductive
coils. The heat can be applied from at least one side or more than one side,
can be
continuous or periodic and can be for only a portion of the material or all
the material.
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For example, a portion of the conveying trough can be heated by use of a
heating jacket.
Heating can be, for example, for the purpose of drying the material. In the
case of drying
the material, this can also be facilitated, with or without heating, by the
movement of a
gas (e.g., air, oxygen, nitrogen, He, CO2, Argon) over and/or through the
biomass as it is
being conveyed.
[00100] Optionally, pre-treatment processing can include cooling the material.
Cooling material is described in U.S. Pat. No. 7,900,857 to Medoff, the
disclosure of
which in incorporated herein by reference. For example, cooling can be by
supplying a
cooling fluid, for example water (e.g., with glycerol), or nitrogen (e.g.,
liquid nitrogen) to
the bottom of the conveying trough. Alternatively, a cooling gas, for example,
chilled
nitrogen can be blown over the biomass materials or under the conveying
system.
[00101] Another optional pre-treatment processing method can include adding a
material to the biomass or other feedstocks. The additional material can be
added by, for
example, by showering, sprinkling and or pouring the material onto the biomass
as it is
conveyed. Materials that can be added include, for example, metals, ceramics
and/or
ions as described in U.S. Pat. App. Pub. 2010/0105119 Al (filed October 26,
2009) and
U.S. Pat. App. Pub. 2010/0159569 Al (filed December 16, 2009), the entire
disclosures
of which are incorporated herein by reference. Optional materials that can be
added
include acids and bases. Other materials that can be added are oxidants (e.g.,
peroxides,
chlorates), polymers, polymerizable monomers (e.g., containing unsaturated
bonds),
water, catalysts, enzymes and/or organisms. Materials can be added, for
example, in
pure form, as a solution in a solvent (e.g., water or an organic solvent)
and/or as a
solution. In some cases the solvent is volatile and can be made to evaporate
e.g., by
heating and/or blowing gas as previously described. The added material may
form a
uniform coating on the biomass or be a homogeneous mixture of different
components
(e.g., biomass and additional material). The added material can modulate the
subsequent
irradiation step by increasing the efficiency of the irradiation, damping the
irradiation or
changing the effect of the irradiation (e.g., from electron beams to X-rays or
heat). The
method may have no impact on the irradiation but may be useful for further
downstream
processing. The added material may help in conveying the material, for
example, by
lowering dust levels.
[00102] Biomass can be delivered to a conveyor (e.g., vibratory conveyors used
in the
vaults herein described) by a belt conveyor, a pneumatic conveyor, a screw
conveyor, a
hopper, a pipe, manually or by a combination of these. The biomass can, for
example, be
dropped, poured and/or placed onto the conveyor by any of these methods. In
some

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embodiments, the material is delivered to the conveyor using an enclosed
material
distribution system to help maintain a low oxygen atmosphere and/or control
dust and
fines. Lofted or air suspended biomass fines and dust are undesirable because
these can
form an explosion hazard or damage the window foils of an electron gun (if
such a
device is used for treating the material).
[00103] The material can be leveled to form a uniform thickness between about
0.0312 and 5 inches (e.g., between about 0.0625 and 2.000 inches, between
about 0.125
and 1 inches, between about 0.125 and 0.5 inches, between about 0.3 and 0.9
inches,
between about 0.2 and 0.5 inches between about 0.25 and 1.0 inches, between
about 0.25
and 0.5 inches, 0.100 +/- 0.025 inches, 0.150 +/- 0.025 inches, 0.200 +/-
0.025 inches,
0.250 +/- 0.025 inches, 0.300 +/- 0.025 inches, 0.350 +/- 0.025 inches, 0.400
+/- 0.025
inches, 0.450 +/- 0.025 inches, 0.500 +/- 0.025 inches, 0.550 +/- 0.025
inches, 0.600 +/-
0.025 inches, 0.700 +/- 0.025 inches, 0.750 +/- 0.025 inches, 0.800 +/- 0.025
inches,
0.850 +/- 0.025 inches, 0.900 +/- 0.025 inches, 0.900 +/- 0.025 inches.
[00104] Generally, it is preferred to convey the material as quickly as
possible through
the electron beam to maximize throughput. For example, the material can be
conveyed
at rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at
least 4 ft/min, at
least 5 ft/min, at least 10 ft/min, at least 15 ft/min, 20, 25, 30, 35, 40,
45, 50 ft/min. The
rate of conveying is related to the beam current, for example, for a 1/4 inch
thick biomass
and 100 mA, the conveyor can move at about 20 ft/min to provide a useful
irradiation
dosage, at 50 mA the conveyor can move at about 10 ft/min to provide
approximately the
same irradiation dosage.
[00105] After the biomass material has been conveyed through the radiation
zone,
optional post-treatment processing can be done. The optional post-treatment
processing
can, for example, be a process described with respect to the pre-irradiation
processing.
For example, the biomass can be screened, heated, cooled, and/or combined with
additives. Uniquely to post-irradiation, quenching of the radicals can occur,
for example,
quenching of radicals by the addition of fluids or gases (e.g., oxygen,
nitrous oxide,
ammonia, liquids), using pressure, heat, and/or the addition of radical
scavengers. For
example, the biomass can be conveyed out of the enclosed conveyor and exposed
to a
gas (e.g., oxygen) where it is quenched, forming carboxylated groups. In one
embodiment the biomass is exposed during irradiation to the reactive gas or
fluid.
Quenching of biomass that has been irradiated is described in U.S. Pat. No.
8,083,906 to
Medoff, the entire disclosure of which is incorporated herein by reference.
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[00106] If desired, one or more mechanical treatments can be used in addition
to
irradiation to further reduce the recalcitrance of the carbohydrate-containing
material.
These processes can be applied before, during and or after irradiation.
[00107] In some cases, the mechanical treatment may include an initial
preparation of
the feedstock as received, e.g., size reduction of materials, such as by
comminution, e.g.,
cutting, grinding, shearing, pulverizing or chopping. For example, in some
cases, loose
feedstock (e.g., recycled paper, starchy materials, or switchgrass) is
prepared by shearing
or shredding. Mechanical treatment may reduce the bulk density of the
carbohydrate-
containing material, increase the surface area of the carbohydrate-containing
material
and/or decrease one or more dimensions of the carbohydrate-containing
material.
[00108] Alternatively, or in addition, the feedstock material can be treated
with
another treatment, for example chemical treatments, such as an with an acid
(HC1,
H2SO4, H3PO4), a base (e.g., KOH and NaOH), a chemical oxidant (e.g.,
peroxides,
chlorates, ozone), irradiation, steam explosion, pyrolysis, sonication,
oxidation, chemical
treatment. The treatments can be in any order and in any sequence and
combinations. For
example, the feedstock material can first be physically treated by one or more
treatment
methods, e.g., chemical treatment including and in combination with acid
hydrolysis
(e.g., utilizing HC1, H2SO4, H3PO4), radiation, sonication, oxidation,
pyrolysis or steam
explosion, and then mechanically treated. This sequence can be advantageous
since
materials treated by one or more of the other treatments, e.g., irradiation or
pyrolysis,
tend to be more brittle and, therefore, it may be easier to further change the
structure of
the material by mechanical treatment. As another example, a feedstock material
can be
conveyed through ionizing radiation using a conveyor as described herein and
then
mechanically treated. Chemical treatment can remove some or all of the lignin
(for
example chemical pulping) and can partially or completely hydrolyze the
material. The
methods also can be used with pre-hydrolyzed material. The methods also can be
used
with material that has not been pre hydrolyzed The methods can be used with
mixtures of
hydrolyzed and non-hydrolyzed materials, for example with about 50% or more
non-
hydrolyzed material, with about 60% or more non- hydrolyzed material, with
about 70%
or more non-hydrolyzed material, with about 80% or more non-hydrolyzed
material or
even with 90% or more non-hydrolyzed material.
[00109] In addition to size reduction, which can be performed initially and/or
later in
processing, mechanical treatment can also be advantageous for "opening up,"
"stressing," breaking or shattering the carbohydrate-containing materials,
making the
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cellulose of the materials more susceptible to chain scission and/or
disruption of
crystalline structure during the physical treatment.
[00110] Methods of mechanically treating the carbohydrate-containing material
include, for example, milling or grinding. Milling may be performed using, for
example,
a hammer mill, ball mill, colloid mill, conical or cone mill, disk mill, edge
mill, Wiley
mill, grist mill or other mill. Grinding may be performed using, for example,
a
cutting/impact type grinder. Some exemplary grinders include stone grinders,
pin
grinders, coffee grinders, and bun- grinders. Grinding or milling may be
provided, for
example, by a reciprocating pin or other element, as is the case in a pin
mill. Other
mechanical treatment methods include mechanical ripping or tearing, other
methods that
apply pressure to the fibers, and air attrition milling. Suitable mechanical
treatments
further include any other technique that continues the disruption of the
internal structure
of the material that was initiated by the previous processing steps.
[00111] Mechanical feed preparation systems can be configured to produce
streams
with specific characteristics such as, for example, specific maximum sizes,
specific
length-to-width, or specific surface areas ratios. Physical preparation can
increase the
rate of reactions, improve the movement of material on a conveyor, improve the
irradiation profile of the material, improve the radiation uniformity of the
material, or
reduce the processing time required by opening up the materials and making
them more
accessible to processes and/or reagents, such as reagents in a solution.
[00112] The bulk density of feedstocks can be controlled (e.g., increased). In
some
situations, it can be desirable to prepare a low bulk density material, e.g.,
by densifying
the material (e.g., densification can make it easier and less costly to
transport to another
site) and then reverting the material to a lower bulk density state (e.g.,
after transport).
The material can be densified, for example, from less than about 0.2 g/cc to
more than
about 0.9 g/cc (e.g., less than about 0.3 to more than about 0.5 g/cc, less
than about 0.3 to
more than about 0.9 g/cc, less than about 0.5 to more than about 0.9 g/cc,
less than about
0.3 to more than about 0.8 g/cc, less than about 0.2 to more than about 0.5
g/cc). For
example, the material can be densified by the methods and equipment disclosed
in U.S.
Pat. No. 7,932,065 to Medoff and International Publication No. WO 2008/073186
(which was filed October 26, 2007, was published in English, and which
designated the
United States), the full disclosures of which are incorporated herein by
reference.
Densified materials can be processed by any of the methods described herein,
or any
material processed by any of the methods described herein can be subsequently
densified.
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[00113] In some embodiments, the material to be processed is in the form of a
fibrous
material that includes fibers provided by shearing a fiber source. For
example, the
shearing can be performed with a rotary knife cutter.
[00114] For example, a fiber source, e.g., that is recalcitrant or that has
had its
recalcitrance level reduced, can be sheared, e.g., in a rotary knife cutter,
to provide a first
fibrous material. The first fibrous material is passed through a first screen,
e.g., having
an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch), provide a
second
fibrous material. If desired, the fiber source can be cut prior to the
shearing, e.g., with a
shredder. For example, when a paper is used as the fiber source, the paper can
be first
cut into strips that are, e.g., 1/4- to 1/2-inch wide, using a shredder, e.g.,
a counter-
rotating screw shredder, such as those manufactured by Munson (Utica, N.Y.).
As an
alternative to shredding, the paper can be reduced in size by cutting to a
desired size
using a guillotine cutter. For example, the guillotine cutter can be used to
cut the paper
into sheets that are, e.g., 10 inches wide by 12 inches long.
[00115] In some embodiments, the shearing of the fiber source and the passing
of the
resulting first fibrous material through a first screen are performed
concurrently. The
shearing and the passing can also be performed in a batch-type process.
[00116] For example, a rotary knife cutter can be used to concurrently shear
the fiber
source and screen the first fibrous material. A rotary knife cutter includes a
hopper that
can be loaded with a shredded fiber source prepared by shredding a fiber
source.
[00117] In some implementations, the feedstock is physically treated prior to
saccharification and/or fermentation. Physical treatment processes can include
one or
more of any of those described herein, such as mechanical treatment, chemical
treatment,
irradiation, sonication, oxidation, pyrolysis or steam explosion. Treatment
methods can
be used in combinations of two, three, four, or even all of these technologies
(in any
order). When more than one treatment method is used, the methods can be
applied at the
same time or at different times. Other processes that change a molecular
structure of a
biomass feedstock may also be used, alone or in combination with the processes
disclosed herein.
[00118] Mechanical treatments that may be used, and the characteristics of the
mechanically treated carbohydrate-containing materials, are described in
further detail in
U.S. Pat. App. Pub. 2012/0100577 Al, filed October 18, 2011, the full
disclosure of
which is hereby incorporated herein by reference.
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SONICATION, PYROLYSIS, OXIDATION, STEAM EXPLOSION
[00119] If desired, one or more sonication, pyrolysis, oxidative, or steam
explosion
processes can be used instead of or in addition to irradiation to reduce or
further reduce
the recalcitrance of the carbohydrate-containing material. For example, these
processes
can be applied before, during and or after irradiation. These processes are
described in
detail in U.S. Pat. No. 7,932,065 to Medoff, the full disclosure of which is
incorporated
herein by reference.
INTERMEDIATES AND PRODUCTS
[00120] Using the processes described herein, the biomass material can be
converted
to one or more products, such as energy, fuels, foods and materials. For
example,
intermediates and products such as organic acids, salts of organic acids,
anhydrides,
esters of organic acids and fuels, e.g., fuels for internal combustion engines
or feedstocks
for fuel cells. Systems and processes are described herein that can use as
feedstock
cellulosic and/or lignocellulosic materials that are readily available, but
often can be
difficult to process, e.g., municipal waste streams and waste paper streams,
such as
streams that include newspaper, Kraft paper, corrugated paper or mixtures of
these.
[00121] Specific examples of products include, but are not limited to,
hydrogen,
sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose,
disaccharides,
oligosaccharides and polysaccharides), alcohols (e.g., monohydric alcohols or
dihydric
alcohols, such as ethanol, n-propanol, isobutanol, sec-butanol, tert-butanol
or n-butanol),
hydrated or hydrous alcohols (e.g., containing greater than 10%, 20%, 30% or
even
greater than 40% water), biodiesel, organic acids, hydrocarbons (e.g.,
methane, ethane,
propane, isobutene, pentane, n-hexane, biodiesel, bio-gasoline and mixtures
thereof), co-
products (e.g., proteins, such as cellulolytic proteins (enzymes) or single
cell proteins),
and mixtures of any of these in any combination or relative concentration, and
optionally
in combination with any additives (e.g., fuel additives). Other examples
include
carboxylic acids, salts of a carboxylic acid, a mixture of carboxylic acids
and salts of
carboxylic acids and esters of carboxylic acids (e.g., methyl, ethyl and n-
propyl esters),
ketones (e.g., acetone), aldehydes (e.g., acetaldehyde), alpha and beta
unsaturated acids
(e.g., acrylic acid) and olefins (e.g., ethylene). Other alcohols and alcohol
derivatives
include propanol, propylene glycol, 1,4-butanediol, 1,3-propanediol, sugar
alcohols (e.g.,
erythritol, glycol, glycerol, sorbitol threitol, arabitol, ribitol, mannitol,
dulcitol, fucitol,

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iditol, isomalt, maltitol, lactitol, xylitol and other polyols), and methyl or
ethyl esters of
any of these alcohols. Other products include methyl acrylate,
methylmethacrylate, D-
lactic acid, L-lactic acid, pyruvic acid, poly lactic acid,d, citric acid,
formic acid, acetic
acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid,
3-
hydroxypropionic acid, palmitic acid, stearic acid, oxalic acid, malonic acid,
glutaric
acid, oleic acid, linoleic acid, glycolic acid, gamma-hydroxybutyric acid, and
mixtures
thereof, salts of any of these acids, mixtures of any of the acids and their
respective salts.
[00122] Any combination of the above products with each other, and/or of the
above
products with other products, which other products may be made by the
processes
described herein or otherwise, may be packaged together and sold as products.
The
products may be combined, e.g., mixed, blended or co-dissolved, or may simply
be
packaged or sold together.
[00123] Any of the products or combinations of products described herein may
be
sanitized or sterilized prior to selling the products, e.g., after
purification or isolation or
even after packaging, to neutralize one or more potentially undesirable
contaminants that
could be present in the product(s). Such sanitation can be done with electron
bombardment, for example, be at a dosage of less than about 20 Mrad, e.g.,
from about
0.1 to 15 Mrad, from about 0.5 to 7 Mrad, or from about 1 to 3 Mrad.
[00124] The processes described herein can produce various by-product streams
useful for generating steam and electricity to be used in other parts of the
plant (co-
generation) or sold on the open market. For example, steam generated from
burning by-
product streams can be used in a distillation process. As another example,
electricity
generated from burning by-product streams can be used to power electron beam
generators used in pretreatment.
[00125] The by-products used to generate steam and electricity are derived
from a
number of sources throughout the process. For example, anaerobic digestion of
wastewater can produce a biogas high in methane and a small amount of waste
biomass
(sludge). As another example, post-saccharification and/or post-distillate
solids (e.g.,
unconverted lignin, cellulose, and hemicellulose remaining from the
pretreatment and
primary processes) can be used, e.g., burned, as a fuel.
[00126] Other intermediates and products, including food and pharmaceutical
products, are described in U.S. Pat. App. Pub. 2010/0124583 Al, published May
20,
2010, to Medoff, the full disclosure of which is hereby incorporated by
reference herein.
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LIGNIN DERIVED PRODUCTS
[00127] The spent biomass (e.g., spent lignocellulosic material) from
lignocellulosic
processing by the methods described are expected to have a high lignin content
and in
addition to being useful for producing energy through combustion in a Co-
Generation
plant, may have uses as other valuable products. For example, the lignin can
be used as
captured as a plastic, or it can be synthetically upgraded to other plastics.
In some
instances, it can also be converted to lignosulfonates, which can be utilized
as binders,
dispersants, emulsifiers or sequestrants.
[00128] When used as a binder, the lignin or a lignosulfonate can, e.g., be
utilized in
coal briquettes, in ceramics, for binding carbon black, for binding
fertilizers and
herbicides, as a dust suppressant, in the making of plywood and particle
board, for
binding animal feeds, as a binder for fiberglass, as a binder in linoleum
paste and as a
soil stabilizer.
[00129] When used as a dispersant, the lignin or lignosulfonates can be used,
for
example in, concrete mixes, clay and ceramics, dyes and pigments, leather
tanning and in
gypsum board.
[00130] When used as an emulsifier, the lignin or lignosulfonates can be used,
e.g., in
asphalt, pigments and dyes, pesticides and wax emulsions.
[00131] As a sequestrant, the lignin or lignosulfonates can be used, e.g., in
micro-
nutrient systems, cleaning compounds and water treatment systems, e.g., for
boiler and
cooling systems.
[00132] For energy production lignin generally has a higher energy content
than
holocellulose (cellulose and hemicellulose) since it contains more carbon than
homocellulose. For example, dry lignin can have an energy content of between
about
11,000 and 12,500 BTU per pound, compared to 7,000 an 8,000 BTU per pound of
holocellulose. As such, lignin can be densified and converted into briquettes
and pellets
for burning. For example, the lignin can be converted into pellets by any
method
described herein. For a slower burning pellet or briquette, the lignin can be
crosslinked,
such as applying a radiation dose of between about 0.5 Mrad and 5 Mrad.
Crosslinking
can make a slower burning form factor. The form factor, such as a pellet or
briquette,
can be converted to a "synthetic coal" or charcoal by pyrolyzing in the
absence of air,
e.g., at between 400 and 950 C. Prior to pyrolyzing, it can be desirable to
crosslink the
lignin to maintain structural integrity.
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SACCHARIFICATION
[00133] In order to convert the feedstock to a form that can be readily
processed, the
glucan- or xylan-containing cellulose in the feedstock can be hydrolyzed to
low
molecular weight carbohydrates, such as sugars, by a saccharifying agent,
e.g., an
enzyme or acid, a process referred to as saccharification. The low molecular
weight
carbohydrates can then be used, for example, in an existing manufacturing
plant, such as
a single cell protein plant, an enzyme manufacturing plant, or a fuel plant,
e.g., an
ethanol manufacturing facility.
[00134] The feedstock can be hydrolyzed using an enzyme, e.g., by combining
the
materials and the enzyme in a solvent, e.g., in an aqueous solution.
[00135] Alternatively, the enzymes can be supplied by organisms that break
down
biomass, such as the cellulose and/or the lignin portions of the biomass,
contain or
manufacture various cellulolytic enzymes (cellulases), ligninases or various
small
molecule biomass-degrading metabolites. These enzymes may be a complex of
enzymes
that act synergistically to degrade crystalline cellulose or the lignin
portions of biomass.
Examples of cellulolytic enzymes include: endoglucanases, cellobiohydrolases,
and
cellobiases (beta-glucosidases).
[00136] During saccharification a cellulosic substrate can be initially
hydrolyzed by
endoglucanases at random locations producing oligomeric intermediates. These
intermediates are then substrates for exo-splitting glucanases such as
cellobiohydrolase
to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a
water-
soluble 1,4-linked dimer of glucose. Finally, cellobiase cleaves cellobiose to
yield
glucose. The efficiency (e.g., time to hydrolyze and/or completeness of
hydrolysis) of
this process depends on the recalcitrance of the cellulosic material.
[00137] Therefore, the treated biomass materials can be saccharified,
generally by
combining the material and a cellulase enzyme in a fluid medium, e.g., an
aqueous
solution. In some cases, the material is boiled, steeped, or cooked in hot
water prior to
saccharification, as described in U.S. Pat. App. Pub. 2012/0100577 Al by
Medoff and
Masterman, published on April 26, 2012, the entire contents of which are
incorporated
herein.
[00138] The saccharification process can be partially or completely performed
in a
tank (e.g., a tank having a volume of at least 4000, 40,000, or 500,000 L) in
a
manufacturing plant, and/or can be partially or completely performed in
transit, e.g., in a
rail car, tanker truck, or in a supertanker or the hold of a ship. The time
required for
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complete saccharification will depend on the process conditions and the
carbohydrate-
containing material and enzyme used. If saccharification is performed in a
manufacturing plant under controlled conditions, the cellulose may be
substantially
entirely converted to sugar, e.g., glucose in about 12-96 hours. If
saccharification is
performed partially or completely in transit, saccharification may take
longer.
[00139] It is generally preferred that the tank contents be mixed during
saccharification, e.g., using jet mixing as described in International App.
No.
PCT/US2010/035331, filed May 18, 2010, which was published in English as WO
2010/135380 and designated the United States, the full disclosure of which is
incorporated by reference herein.
[00140] The addition of surfactants can enhance the rate of saccharification.
Examples of surfactants include non-ionic surfactants, such as a Tween 20 or
Tween
80 polyethylene glycol surfactants, ionic surfactants, or amphoteric
surfactants.
[00141] It is generally preferred that the concentration of the sugar solution
resulting
from saccharification be relatively high, e.g., greater than 40%, or greater
than 50, 60,
70, 80, 90 or even greater than 95% by weight. Water may be removed, e.g., by
evaporation, to increase the concentration of the sugar solution. This reduces
the volume
to be shipped, and also inhibits microbial growth in the solution.
[00142] Alternatively, sugar solutions of lower concentrations may be used, in
which
case it may be desirable to add an antimicrobial additive, e.g., a broad
spectrum
antibiotic, in a low concentration, e.g., 50 to 150 ppm. Other suitable
antibiotics include
amphotericin B, ampicillin, chloramphenicol, ciprofloxacin, gentamicin,
hygromycin B,
kanamycin, neomycin, penicillin, puromycin, streptomycin. Antibiotics will
inhibit
growth of microorganisms during transport and storage, and can be used at
appropriate
concentrations, e.g., between 15 and 1000 ppm by weight, e.g., between 25 and
500 ppm,
or between 50 and 150 ppm. If desired, an antibiotic can be included even if
the sugar
concentration is relatively high. Alternatively, other additives with anti-
microbial of
preservative properties may be used. Preferably the antimicrobial additive(s)
are food-
grade.
[00143] A relatively high concentration solution can be obtained by limiting
the
amount of water added to the carbohydrate-containing material with the enzyme.
The
concentration can be controlled, e.g., by controlling how much
saccharification takes
place. For example, concentration can be increased by adding more carbohydrate-
containing material to the solution. In order to keep the sugar that is being
produced in
solution, a surfactant can be added, e.g., one of those discussed above.
Solubility can
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also be increased by increasing the temperature of the solution. For example,
the
solution can be maintained at a temperature of 40-50 C, 60-80 C, or even
higher.
SACCHARIFYING AGENTS
[00144] Suitable cellulolytic enzymes include cellulases from species in the
genera
Bacillus, Coprinus, Myceliophthora, Cephalosporium, Scytalidium, Penicillium,
Aspergillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium,
Chrysosporium and Trichoderma, especially those produced by a strain selected
from the
species Aspergillus (see, e.g., EP Pub. No. 0 458 162), Humicola insolens
(reclassified as
Scytalidium thermophilum, see, e.g., U.S. Pat. No. 4,435,307), Coprinus
cinereus,
Fusarium oxysporum, Myceliophthora the rmophila, Meripilus giganteus,
Thielavia
terrestris, Acremonium sp. (including, but not limited to, A. persicinum, A.
acremonium,
A. brachypenium, A. dichromosporum, A. obclavatum, A. pinkertoniae, A.
roseogriseum,
A. incoloratum, and A. furatum). Preferred strains include Humicola insolens
DSM
1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65,
Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS
265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU 9519,
Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium
dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium
pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium
incoloratum CBS 146.62, and Acremonium furatum CBS 299.70H. Cellulolytic
enzymes may also be obtained from Chrysosporium, preferably a strain of
Chrysosporium lucknowense. Additional strains that can be used include, but
are not
limited to, Trichoderma (particularly T viride, T reesei, and T koningii),
alkalophilic
Bacillus (see, for example, U.S. Pat. No. 3,844,890 and EP Pub. No. 0 458
162), and
Streptomyces (see, e.g., EP Pub. No. 0 458 162).
[00145] In addition to or in combination to enzymes, acids, bases and other
chemicals
(e.g., oxidants) can be utilized to saccharify lignocellulosic and cellulosic
materials.
These can be used in any combination or sequence (e.g., before, after and/or
during
addition of an enzyme). For example, strong mineral acids can be utilized
(e.g. HC1,
H2504, H3PO4) and strong bases (e.g., NaOH, KOH).

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SUGARS
[00146] In the processes described herein, for example after saccharification,
sugars
(e.g., glucose and xylose) can be isolated. For example, sugars can be
isolated by
precipitation, crystallization, chromatography (e.g., simulated moving bed
chromatography, high pressure chromatography), centrifugation, extraction, any
other
isolation method known in the art, and combinations thereof.
HYDROGENATION AND OTHER CHEMICAL TRANSFORMATIONS
[00147] The processes described herein can include hydrogenation. For example,
glucose and xylose can be hydrogenated to sorbitol and xylitol respectively.
Hydrogenation can be accomplished by use of a catalyst (e.g., Pt/gamma-A1203,
Ru/C,
Raney Nickel, or other catalysts know in the art) in combination with H2 under
high
pressure (e.g., 10 to 12000 psi). Other types of chemical transformation of
the products
from the processes described herein can be used, for example, production of
organic
sugar derived products such (e.g., furfural and furfural-derived products).
Chemical
transformations of sugar derived products are described in USSN 13/934,704
filed July
3, 2013, the entire disclosure of which is incorporated herein by reference in
its entirety.
FERMENTATION
[00148] Yeast and Zymomonas bacteria, for example, can be used for
fermentation or
conversion of sugar(s) to alcohol(s). Other microorganisms are discussed
below. The
optimum pH for fermentations is about pH 4 to 7. For example, the optimum pH
for
yeast is from about pH 4 to 5, while the optimum pH for Zymomonas is from
about pH 5
to 6. Typical fermentation times are about 24 to 168 hours (e.g., 24 to 96
hrs) with
temperatures in the range of 20 C to 40 C (e.g., 26 C to 40 C), however
thermophilic
microorganisms prefer higher temperatures.
[00149] In some embodiments, e.g., when anaerobic organisms are used, at least
a
portion of the fermentation is conducted in the absence of oxygen, e.g., under
a blanket
of an inert gas such as N2, Ar, He, CO2 or mixtures thereof. Additionally, the
mixture
may have a constant purge of an inert gas flowing through the tank during part
of or all
of the fermentation. In some cases, anaerobic conditions can be achieved or
maintained
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by carbon dioxide production during the fermentation and no additional inert
gas is
needed.
[00150] In some embodiments, all or a portion of the fermentation process can
be
interrupted before the low molecular weight sugar is completely converted to a
product
(e.g., ethanol). The intermediate fermentation products include sugar and
carbohydrates
in high concentrations. The sugars and carbohydrates can be isolated via any
means
known in the art. These intermediate fermentation products can be used in
preparation of
food for human or animal consumption. Additionally or alternatively, the
intermediate
fermentation products can be ground to a fine particle size in a stainless-
steel laboratory
mill to produce a flour-like substance. Jet mixing may be used during
fermentation, and
in some cases saccharification and fermentation are performed in the same
tank.
[00151] Nutrients for the microorganisms may be added during saccharification
and/or fermentation, for example, the food-based nutrient packages described
in U.S.
Pat. App. Pub. 2012/0052536, filed July 15, 2011, the complete disclosure of
which is
incorporated herein by reference.
[00152] "Fermentation" includes the methods and products that are disclosed in
application Nos. PCT/US2012/71093 published June 27, 2013, PCT/ US2012/71907
published June 27, 2012, and PCT/US2012/71083 published June 27, 2012 the
contents
of which are incorporated by reference herein in their entirety.
[00153] Mobile fermenters can be utilized, as described in International App.
No.
PCT/US2007/074028 (which was filed July 20, 2007, was published in English as
WO
2008/011598 and designated the United States) and has a U.S. issued Patent No.
8,318,453, the contents of which are incorporated herein in its entirety.
Similarly, the
saccharification equipment can be mobile. Further, saccharification and/or
fermentation
may be performed in part or entirely during transit.
FERMENTATION AGENTS
[00154] The microorganism(s) used in fermentation can be naturally-occurring
microorganisms and/or engineered microorganisms. For example, the
microorganism
can be a bacterium (including, but not limited to, e.g., a cellulolytic
bacterium), a fungus,
(including, but not limited to, e.g., a yeast), a plant, a protist, e.g., a
protozoa or a fungus-
like protest (including, but not limited to, e.g., a slime mold), or an alga.
When the
organisms are compatible, mixtures of organisms can be utilized.
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[00155] Suitable fermenting microorganisms have the ability to convert
carbohydrates, such as glucose, fructose, xylose, arabinose, mannose,
galactose,
oligosaccharides or polysaccharides into fermentation products. Fermenting
microorganisms include strains of the genus Saccharomyces spp. (including, but
not
limited to, S. cerevisiae (baker's yeast), S. distaticus, S. uvarum), the
genus
Kluyveromyces, (including, but not limited to, K marxianus, K fragilis), the
genus
Candida (including, but not limited to, C. pseudotropicalis, and C.
brassicae), Pichia
stipitis (a relative of Candida shehatae), the genus Clavispora (including,
but not limited
to, C. lusitaniae and C. opuntiae), the genus Pachysolen (including, but not
limited to, P.
tannophilus), the genus Bretannomyces (including, but not limited to, e.g., B.
clausenii
(Philippidis, G. P., 1996, Cellulose bioconversion technology, in Handbook on
Bioethanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis,
Washington, DC, 179-212)). Other suitable microorganisms include, for example,
Zymomonas mobilis, Clostridium spp. (including, but not limited to, C. the
rmocellum
(Philippidis, 1996, supra), C. saccharobutylacetonicum, C. tyrobutyricum C.
saccharobutylicum, C. Puniceum, C. beijemckii, and C. acetobutylicum),
Moniliella spp.
(including but not limited to M. pollinis,M. tomentosa, M. madida, M.
nigrescens, M.
oedocephali, M. megachiliensis), Yarrowia lipolytica, Aureobasidium sp.,
Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp.,
Moniliellaacetoabutans
sp., Typhula variabilis, Candida magnoliae, Ustilaginomycetes sp., Pseudozyma
tsukubaensis, yeast species of genera Zygosaccharomyces, Debaryomyces,
Hansenula
and Pichia, and fungi of the dematioid genus Torula (e.g., T corallina).
[00156] Additional microorganisms include the Lactobacillus group. Examples
include Lactobacillus casei, Lactobacillus rhamnosus, Lactobacillus
delbrueckii,
Lactobacillus plantarum, Lactobacillus coryniformis, e.g., Lactobacillus
coryniformis
subspecies torquens, Lactobacillus pentosus, Lactobacillus brevis. Other
microorganisms include Pediococus penosaceus, Rhizopus oryzae.
[00157] Several organisms, such as bacteria, yeasts and fungi, can be utilized
to
ferment biomass derived products such as sugars and alcohols to succinic acid
and
similar products. For example, organisms can be selected from; Actinobacillus
succinogenes, Anaerobiospirillum succiniciproducens, Mannheimia
succiniciproducens,
Ruminococcus flaverfaciens, Ruminococcus albus, Fibrobacter
succinogenes, Bacteroides fragilis, Bacteroides ruminicola, Bacteroides
amylophilus,Bacteriodes succinogenes, Mannheimia succiniciproducens,
Corynebacterium glutamicum, Aspergillus niger, Aspergillus fumigatus,
Byssochlamys
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nivea, Lentinus degener, Paecilomyces varioti, Penicillium viniferum,
Saccharomyces
cerevisiae, Enterococcus faecali, Prevotella ruminicolas, Debaryomyces
hansenii,
Candida catenulata VKM Y-5, C. mycoderma VKM Y-240, C. rugosa VKM Y-67, C.
paludigena VKM Y-2443, C. utilis VKM Y-74, C. utilis 766, C. zeylanoides VKM Y-
6,
C. zeylanoides VKM Y-14, C. zeylanoides VKM Y-2324, C. zeylanoides VKM Y-1543,
C. zeylanoides VKM Y-2595, C. valida VKM Y-934, Kluyveromyces wickerhamii VKM
Y-589, Pichia anomala VKM Y-118, P. besseyi VKM Y-2084, P. media VKM Y-1381,
P. guilliermondii H-P-4, P. guilliermondii 916, P. inositovora VKM Y-2494,
Saccharomyces cerevisiae VKM Y-381, Torulopsis candida 127, T candida 420,
Yarrowia lipolytica 12a, Y. lipolytica VKM Y-47, Y. lipolytica 69, Y.
lipolytica VKM Y-
57, Y. lipolytica 212, Y. lipolytica 374/4, Y. lipolytica 585, Y. lipolytica
695, Y. lipolytica
704, and mixtures of these organisms.
[00158] Many such microbial strains are publicly available, either
commercially or
through depositories such as the ATCC (American Type Culture Collection,
Manassas,
Virginia, USA), the NRRL (Agricultural Research Service Culture Collection,
Peoria,
Illinois, USA), or the DSMZ (Deutsche Sammlung von Mikroorganismen und
Zellkulturen GmbH, Braunschweig, Germany), to name a few.
[00159] Commercially available yeasts include, for example, RED STAR /Lesaffre
Ethanol Red (available from Red Star/Lesaffre, USA), FALI (available from
Fleischmann's Yeast, a division of Bums Philip Food Inc., USA), SUPERSTART
(available from Alltech, now Lalemand), GERT STRAND (available from Gert
Strand
AB, Sweden) and FERMOL (available from DSM Specialties).
DISTILLATION
[00160] After fermentation, the resulting fluids can be distilled using, for
example, a
"beer column" to separate ethanol and other alcohols from the majority of
water and
residual solids. The vapor exiting the beer column can be, e.g., 35% by weight
ethanol
and can be fed to a rectification column. A mixture of nearly azeotropic
(92.5%) ethanol
and water from the rectification column can be purified to pure (99.5%)
ethanol using
vapor-phase molecular sieves. The beer column bottoms can be sent to the first
effect of
a three-effect evaporator. The rectification column reflux condenser can
provide heat for
this first effect. After the first effect, solids can be separated using a
centrifuge and dried
in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled
to
fermentation and the rest sent to the second and third evaporator effects.
Most of the
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evaporator condensate can be returned to the process as fairly clean
condensate with a
small portion split off to waste water treatment to prevent build-up of low-
boiling
compounds.
HYDROCARBON-CONTAINING MATERIALS
[00161] In other embodiments utilizing the methods and systems described
herein,
hydrocarbon-containing materials can be processed. Any process described
herein can be
used to treat any hydrocarbon-containing material herein described.
"Hydrocarbon-
containing materials," as used herein, is meant to include oil sands, oil
shale, tar sands,
coal dust, coal slurry, bitumen, various types of coal, and other naturally-
occurring and
synthetic materials that include both hydrocarbon components and solid matter.
The
solid matter can include rock, sand, clay, stone, silt, drilling slurry, or
other solid organic
and/or inorganic matter. The term can also include waste products such as
drilling waste
and by-products, refining waste and by-products, or other waste products
containing
hydrocarbon components, such as asphalt shingling and covering, asphalt
pavement, etc.
[00162] In yet other embodiments utilizing the methods and systems described
herein,
wood and wood containing produces can be processed. For example, lumber
products
can be processed, e.g. boards, sheets, laminates, beams, particle boards,
composites,
rough cut wood, soft wood and hard wood. In addition cut trees, bushes, wood
chips, saw
dust, roots, bark, stumps, decomposed wood and other wood containing biomass
material
can be processed.
CONVEYING SYSTEMS
[00163] Various conveying systems can be used to convey the biomass material,
for
example, as discussed, to a vault, and under an electron beam in a vault.
Exemplary
conveyors are belt conveyors, pneumatic conveyors, screw conveyors, carts,
trains, trains
or carts on rails, elevators, front loaders, backhoes, cranes, various
scrapers and shovels,
trucks, and throwing devices can be used. For example, vibratory conveyors can
be used
in various processes described herein. Vibratory conveyors are described in
PCT/US2013/64289 filed October 10, 2013 the full disclosure of which is
incorporated
by reference herein.
[00164] Vibratory conveyors are particularly useful for spreading the material
and
producing a uniform layer on the conveyor trough surface. For example the
initial

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feedstock can form a pile of material that can be at least four feet high
(e.g., at least
about 3 feet, at least about 2 feet, at least about 1 foot, at least about 6
inches, at least
about 5 inches, at least about, 4 inches, at least about 3 inches, at least
about 2 inches, at
least about 1 inch, at least about 1/2 inch) and spans less than the width of
the conveyor
(e.g., less than about 10%, less than about 20%, less than about 30%, less
than about
40%, less than about 50%, less than about 60%, less than about 70%, less than
about
80%, less than about 90%, less than about 95%, less than about 99%). The
vibratory
conveyor can spread the material to span the entire width of the conveyor
trough and
have a uniform thickness, preferably as discussed above. In some cases, an
additional
spreading method can be useful. For example, a spreader such as a broadcast
spreader, a
drop spreader (e.g., a CHRISTY SPREADERTM) or combinations thereof can be used
to
drop (e.g., place, pour, spill and/or sprinkle) the feedstock over a wide
area. Optionally,
the spreader can deliver the biomass as a wide shower or curtain onto the
vibratory
conveyor. Additionally, a second conveyor, upstream from the first conveyor
(e.g., the
first conveyor is used in the irradiation of the feedstock), can drop biomass
onto the first
conveyor, where the second conveyor can have a width transverse to the
direction of
conveying smaller than the first conveyor. In particular, when the second
conveyor is a
vibratory conveyor, the feedstock is spread by the action of the second and
first
conveyor. In some optional embodiments, the second conveyor ends in a bias
cross cut
discharge (e.g., a bias cut with a ratio of 4:1) so that the material can be
dropped as a
wide curtain (e.g., wider than the width of the second conveyor) onto the
first conveyor.
The initial drop area of the biomass by the spreader (e.g., broadcast
spreader, drop
spreader, conveyor, or cross cut vibratory conveyor) can span the entire width
of the first
vibratory conveyor, or it can span part of this width. Once dropped onto the
conveyor,
the material is spread even more uniformly by the vibrations of the conveyor
so that,
preferably, the entire width of the conveyor is covered with a uniform layer
of biomass.
In some embodiments combinations of spreaders can be used. Some methods of
spreading a feed stock are described in U.S. Patent No. 7,153,533, filed July
23, 2002
and published December 26, 2006, the entire disclosure of which is
incorporated herein
by reference.
[00165] Generally, it is preferred to convey the material as quickly as
possible through
an electron beam to maximize throughput. For example, the material can be
conveyed at
rates of at least 1 ft/min, e.g., at least 2 ft/min, at least 3 ft/min, at
least 4 ft/min, at least 5
ft/min, at least 10 ft/min, at least 15 ft/min, at least 20 ft/min, at least
25 ft/min, at least
30 ft/min, at least 40 ft/min, at least 50 ft/min, at least 60 ft/min, at
least 70 ft/min, at
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least 80 ft/min, at least 90 ft/min. The rate of conveying is related to the
beam current
and targeted irradiation dose, for example, for a 1/4 inch thick biomass
spread over a 5.5
foot wide conveyor and 100 mA, the conveyor can move at about 20 ft/min to
provide a
useful irradiation dosage (e.g. about 10 Mrad for a single pass), at 50 mA the
conveyor
can move at about 10 ft/min to provide approximately the same irradiation
dosage.
[00166] The rate at which material can be conveyed depends on the shape and
mass of
the material being conveyed, and the desired treatment. Flowing materials
e.g.,
particulate materials, are particularly amenable to conveying with vibratory
conveyors.
Conveying speeds can, for example be, at least 100 lb/hr (e.g., at least 500
lb/hr, at least
1000 lb/hr, at least 2000 lb/hr, at least 3000 lb/hr, at least 4000 lb/hr, at
least 5000 lb/hr,
at least 10,000 lb/hr, at least 15, 000 lb/hr, or even at least 25,000 lb/hr).
Some typical
conveying speeds can be between about 1000 and 10,000 lb/hr, (e.g., between
about
1000 lb/hr and 8000 lb/hr, between about 2000 and 7000 lb/hr, between about
2000 and
6000 lb/hr, between about 2000 and 50001b/hr, between about 2000 and 4500
lb/hr,
between about 1500 and 5000 lb/hr, between about 3000 and 7000 lb/hr, between
about
3000 and 6000 lb/hr, between about 4000 and 6000 lb/hr and between about 4000
and
5000 lb/hr). Typical conveying speeds depend on the density of the material.
For
example, for a biomass with a density of about 35 lb/ft3, and a conveying
speed of about
5000 lb/hr, the material is conveyed at a rate of about 143 ft3/hr, if the
material is '4"
thick and is in a trough 5.5 ft wide, the material is conveyed at a rate of
about 1250 ft/hr
(about 21 ft/min). Rates of conveying the material can therefore vary greatly.
Preferably,
for example, a 1/4" thick layer of biomass, is conveyed at speeds of between
about 5 and
100 ft/min (e.g. between about 5 and 100 ft/min, between about 6 and 100
ft/min,
between about 7 and 100 ft/min, between about 8 and 100 ft/min, between about
9 and
100 ft/min, between about 10 and 100 ft/min, between about 11 and 100 ft/min,
between
about 12 and 100 ft/min, between about 13 and 100 ft/min, between about 14 and
100
ft/min, between about 15 and 100 ft/min, between about 20 and 100 ft/min,
between
about 30 and 100 ft/min, between about 40 and 100 ft/min, between about 2 and
60
ft/min, between about 3 and 60 ft/min, between about 5 and 60 ft/min, between
about 6
and 60 ft/min, between about 7 and 60 ft/min, between about 8 and 60 ft/min,
between
about 9 and 60 ft/min, between about 10 and 60 ft/min, between about 15 and 60
ft/min,
between about 20 and 60 ft/min, between about 30 and 60 ft/min, between about
40 and
60 ft/min, between about 2 and 50 ft/min, between about 3 and 50 ft/min,
between about
and 50 ft/min, between about 6 and 50 ft/min, between about 7 and 50 ft/min,
between
about 8 and 50 ft/min, between about 9 and 50 ft/min, between about 10 and 50
ft/min,
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between about 15 and 50 ft/min, between about 20 and 50 ft/min, between about
30 and
50 ft/min, between about 40 and 50 ft/min). It is preferable that the material
be conveyed
at a constant rate, for example, to help maintain a constant irradiation of
the material as it
passes under the electron beam (e.g., shower, field).
[00167] The vibratory conveyors described can include screens used for sieving
and
sorting materials. Port openings on the side or bottom of the troughs can be
used for
sorting, selecting or removing specific materials, for example, by size or
shape. Some
conveyors have counterbalances to reduce the dynamic forces on the support
structure.
Some vibratory conveyors are configured as spiral elevators, are designed to
curve
around surfaces and/or are designed to drop material from one conveyor to
another (e.g.,
in a step, cascade or as a series of steps or a stair). Along with conveying
materials
conveyors can be used, by themselves or coupled with other equipment or
systems, for
screening, separating, sorting, classifying, distributing, sizing, inspection,
picking, metal
removing, freezing, blending, mixing, orienting, heating, cooking, drying,
dewatering,
cleaning, washing, leaching, quenching, coating, de-dusting and/or feeding.
The
conveyors can also include covers (e.g., dust-tight covers), side discharge
gates, bottom
discharge gates, special liners (e.g., anti-stick, stainless steel, rubber,
custom steal, and or
grooved), divided troughs, quench pools, screens, perforated plates, detectors
(e.g., metal
detectors), high temperature designs, food grade designs, heaters, dryers and
or coolers.
In addition, the trough can be of various shapes, for example, flat bottomed,
vee shaped
bottom, flanged at the top, curved bottom, flat with ridges in any direction,
tubular, half
pipe, covered or any combinations of these. In particular, the conveyors can
be coupled
with an irradiation systems and/or equipment.
[00168] The conveyors (e.g., vibratory conveyor) can be made of corrosion
resistant
materials. The conveyors can utilize structural materials that include
stainless steel (e.g.,
304, 316 stainless steel, HASTELLOY ALLOYS and INCONEL Alloys). For
example, HASTELLOY Corrosion-Resistant alloys from Hynes (Kokomo, Indiana,
USA) such as HASTELLOY B-3 ALLOY, HASTELLOY HYBRID-BC1
ALLOY, HASTELLOY C-4 ALLOY, HASTELLOY C-22 ALLOY,
HASTELLOY C-22115 ALLOY, HASTELLOY C-276 ALLOY, HASTELLOY
C-2000 ALLOY, HASTELLOY G-30 ALLOY, HASTELLOY G-35 ALLOY,
HASTELLOY N ALLOY and HASTELLOY ULTIMET alloy.
[00169] The vibratory conveyors can include non-stick release coatings, for
example,
TUFFLONTm (Dupont, Delaware, USA). The vibratory conveyors can also include
corrosion resistant coatings. For example, coatings that can be supplied from
Metal
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Coatings Corp (Houston, Texas, USA) and others such as Fluoropolymer, XYLAN ,
Molybdenum Disulfide, Epoxy Phenolic, Phosphate- ferrous metal coating,
Polyurethane- high gloss topcoat for epoxy, inorganic zinc, Poly Tetrafluoro
ethylene,
PPS/RYTON , fluorinated ethylene propylene, PVDF/DYKOR , ECTFE/HALAR
and Ceramic Epoxy Coating. The coatings can improve resistance to process
gases (e.g.,
ozone), chemical corrosion, pitting corrosion, galling corrosion and
oxidation.
[00170] Optionally, in addition to the conveying systems described herein, one
or
more other conveying systems can be enclosed. When using an enclosure, the
enclosed
conveyor can also be purged with an inert gas so as to maintain an atmosphere
at a
reduced oxygen level. Keeping oxygen levels low avoids the formation of ozone
which
in some instances is undesirable due to its reactive and toxic nature. For
example, the
oxygen can be less than about 20% (e.g., less than about 10%, less than about
1%, less
than about 0.1%, less than about 0.01%, or even less than about 0.001%
oxygen).
Purging can be done with an inert gas including, but not limited to, nitrogen,
argon,
helium or carbon dioxide. This can be supplied, for example, from a boil off
of a liquid
source (e.g., liquid nitrogen or helium), generated or separated from air in
situ, or
supplied from tanks. The inert gas can be recirculated and any residual oxygen
can be
removed using a catalyst, such as a copper catalyst bed. Alternatively,
combinations of
purging, recirculating and oxygen removal can be done to keep the oxygen
levels low.
[00171] The enclosed conveyor can also be purged with a reactive gas that can
react
with the biomass. This can be done before, during or after the irradiation
process. The
reactive gas can be, but is not limited to, nitrous oxide, ammonia, oxygen,
ozone,
hydrocarbons, aromatic compounds, amides, peroxides, azides, halides,
oxyhalides,
phosphides, phosphines, arsines, sulfides, thiols, boranes and/or hydrides.
The reactive
gas can be activated in the enclosure, e.g., by irradiation (e.g., electron
beam, UV
irradiation, microwave irradiation, heating, IR radiation), so that it reacts
with the
biomass. The biomass itself can be activated, for example by irradiation.
Preferably the
biomass is activated by the electron beam, to produce radicals which then
react with the
activated or unactivated reactive gas, e.g., by radical coupling or quenching.
[00172] Purging gases supplied to an enclosed conveyor can also be cooled, for
example below about 25 C, below about 0 C, below about -40 C, below about -80
C,
below about -120 C. For example, the gas can be boiled off from a compressed
gas such
as liquid nitrogen or sublimed from solid carbon dioxide. As an alternative
example, the
gas can be cooled by a chiller or part of or the entire conveyor can be
cooled.
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OTHER EMBODIMENTS
[00173] Any material, processes or processed materials discussed herein can be
used
to make products and/or intermediates such as composites, fillers, binders,
plastic
additives, adsorbents and controlled release agents. The methods can include
densification, for example, by applying pressure and heat to the materials.
For example,
composites can be made by combining fibrous materials with a resin or polymer.
For
example, radiation cross-linkable resin, e.g., a thermoplastic resin can be
combined with
a fibrous material to provide a fibrous material/cross-linkable resin
combination. Such
materials can be, for example, useful as building materials, protective
sheets, containers
and other structural materials (e.g., molded and/or extruded products).
Absorbents can
be, for example, in the form of pellets, chips, fibers and/or sheets.
Adsorbents can be
used, for example, as pet bedding, packaging material or in pollution control
systems.
Controlled release matrices can also be the form of, for example, pellets,
chips, fibers
and or sheets. The controlled release matrices can, for example, be used to
release drugs,
biocides, fragrances. For example, composites, absorbents and control release
agents
and their uses are described in International Serial No. PCT/US2006/010648,
filed
March 23, 2006, and U.S. Patent No. 8,074,910 filed November 22, 2011, the
entire
disclosures of which are herein incorporated by reference.
[00174] In some instances the biomass material is treated at a first level to
reduce
recalcitrance, e.g., utilizing accelerated electrons, to selectively release
one or more
sugars (e.g., xylose). The biomass can then be treated to a second level to
release one or
more other sugars (e.g., glucose). Optionally the biomass can be dried between
treatments. The treatments can include applying chemical and biochemical
treatments to
release the sugars. For example, a biomass material can be treated to a level
of less than
about 20 Mrad (e.g., less than about 15 Mrad, less than about 10 Mrad, less
than about 5
Mrad, less than about 2 Mrad) and then treated with a solution of sulfuric
acid,
containing less than 10% sulfuric acid (e.g., less than about 9%, less than
about 8%, less
than about 7%, less than about 6%, less than about 5%, less than about 4%,
less than
about 3%, less than about 2%, less than about 1%, less than about 0.75%, less
than about
0.50 %, less than about 0.25%) to release xylose. Xylose, for example, that is
released
into solution, can be separated from solids and optionally the solids washed
with a
solvent/solution (e.g., with water and/or acidified water). Optionally, the
solids can be
dried, for example in air and/or under vacuum optionally with heating (e.g.,
below about
150 deg C, below about 120 deg C) to a water content below about 25 wt% (below
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20 wt.%, below about 15 wt.%, below about 10 wt.%, below about 5 wt.%). The
solids
can then be treated with a level of less than about 30 Mrad (e.g., less than
about 25 Mrad,
less than about 20 Mrad, less than about 15 Mrad, less than about 10 Mrad,
less than
about 5 Mrad, less than about 1 Mrad or even not at all) and then treated with
an enzyme
(e.g., a cellulase) to release glucose. The glucose (e.g., glucose in
solution) can be
separated from the remaining solids. The solids can then be further processed,
for
example, utilized to make energy or other products (e.g., lignin derived
products).
FLAVORS, FRAGRANCES AND COLORANTS
[00175] Any of the products and/or intermediates described herein, for
example,
produced by the processes, systems and/or equipment described herein, can be
combined
with flavors, fragrances, colorants and/or mixtures of these. For example, any
one or
more of (optionally along with flavors, fragrances and/or colorants) sugars,
organic
acids, fuels, polyols, such as sugar alcohols, biomass, fibers and composites
can be
combined with (e.g., formulated, mixed or reacted) or used to make other
products. For
example, one or more such product can be used to make soaps, detergents,
candies,
drinks (e.g., cola, wine, beer, liquors such as gin or vodka, sports drinks,
coffees, teas),
syrups, pharmaceuticals, adhesives, sheets (e.g., woven, none woven, filters,
tissues)
and/or composites (e.g., boards). For example, one or more such product can be
combined with herbs, flowers, petals, spices, vitamins, potpourri, or candles.
For
example, the formulated, mixed or reacted combinations can have
flavors/fragrances of
grapefruit, orange, apple, raspberry, banana, lettuce, celery, cinnamon,
chocolate, vanilla,
peppermint, mint, onion, garlic, pepper, saffron, ginger, milk, wine, beer,
tea, lean beef,
fish, clams, olive oil, coconut fat, pork fat, butter fat, beef bouillon,
legume, potatoes,
marmalade, ham, coffee and cheeses.
[00176] Flavors, fragrances and colorants can be added in any amount, such as
between about 0.001 wt.% to about 30 wt.%, e.g., between about 0.01 to about
20,
between about 0.05 to about 10, or between about 0.1 wt.% to about 5 wt.%.
These can
be formulated, mixed and or reacted (e.g., with any one of more product or
intermediate
described herein) by any means and in any order or sequence (e.g., agitated,
mixed,
emulsified, gelled, infused, heated, sonicated, and/or suspended). Fillers,
binders,
emulsifier, antioxidants can also be utilized, for example protein gels,
starches and silica.
[00177] In one embodiment the flavors, fragrances and colorants can be
added to the
biomass immediately after the biomass is irradiated such that the reactive
sites created by
51

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the irradiation may react with reactive compatible sites of the flavors,
fragrances, and
colorants.
[00178] The flavors, fragrances and colorants can be natural and/or synthetic
materials. These materials can be one or more of a compound, a composition or
mixtures
of these (e.g., a formulated or natural composition of several compounds).
Optionally the
flavors, fragrances, antioxidants and colorants can be derived biologically,
for example,
from a fermentation process (e.g., fermentation of saccharified materials as
described
herein). Alternatively, or additionally these flavors, fragrances and
colorants can be
harvested from a whole organism (e.g., plant, fungus, animal, bacteria or
yeast) or a part
of an organism. The organism can be collected and or extracted to provide
color, flavors,
fragrances and/or antioxidant by any means including utilizing the methods,
systems and
equipment described herein, hot water extraction, supercritical fluid
extraction, chemical
extraction (e.g., solvent or reactive extraction including acids and bases),
mechanical
extraction (e.g., pressing, comminuting, filtering), utilizing an enzyme,
utilizing a
bacteria such as to break down a starting material, and combinations of these
methods.
The compounds can be derived by a chemical reaction, for example, the
combination of
a sugar (e.g., as produced as described herein) with an amino acid (Maillard
reaction).
The flavor, fragrance, antioxidant and/or colorant can be an intermediate and
or product
produced by the methods, equipment or systems described herein, for example,
and ester
and a lignin derived product.
[00179] Some examples of flavor, fragrances or colorants are polyphenols.
Polyphenols are pigments responsible for the red, purple and blue colorants of
many
fruits, vegetables, cereal grains, and flowers. Polyphenols also can have
antioxidant
properties and often have a bitter taste. The antioxidant properties make
these important
preservatives. On class of polyphenols are the flavonoids, such as
Anthocyanidines,
flavanonols, flavan-3-ols, s, flavanones and flavanonols. Other phenolic
compounds that
can be used include phenolic acids and their esters, such as chlorogenic acid
and
polymeric tannins.
[00180] Among the colorants inorganic compounds, minerals or organic compounds
can be used, for example titanium dioxide, zinc oxide, aluminum oxide, cadmium
yellow
(E.g., CdS), cadmium orange (e.g., CdS with some Se), alizarin crimson (e.g.,
synthetic
or non-synthetic rose madder), ultramarine (e.g., synthetic ultramarine,
natural
ultramarine, synthetic ultramarine violet), cobalt blue, cobalt yellow, cobalt
green,
viridian (e.g., hydrated chromium(III)oxide), chalcophylite, conichalcite,
cornubite,
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cornwallite and liroconite. Black pigments such as carbon black and self-
dispersed
blacks may be used.
[00181] Some flavors and fragrances that can be utilized include ACALEA TBHQ,
ACET C-6, ALLYL AMYL GLYCOLATE, ALPHA TERPINEOL, AMBRETTOLIDE,
AMBRINOL 95, ANDRANE, APHERMATE, APPLELIDE, BACDANOL ,
BERGAMAL, BETA IONONE EPDXIDE, BETA NAPHTHYL ISO-BUTYL ETHER,
BICYCLONONALACTONE, BORNAFIX , CANTHOXAL, CASHMERAN ,
CASHMERAN VELVET, CASSIFFIX , CEDRAFIX, CEDRAMBER , CEDRYL
ACETATE, CELESTOLIDE, CINNAMALVA, CITRAL DIMETHYL ACETATE,
CITROLATETm, CITRONELLOL 700, CITRONELLOL 950, CITRONELLOL
COEUR, CITRONELLYL ACETATE, CITRONELLYL ACETATE PURE,
CITRONELLYL FORMATE, CLARYCET, CLONAL, CONIFERAN, CONIFERAN
PURE, CORTEX ALDEHYDE 50% PEOMOSA, CYCLABUTE, CYCLACET ,
CYCLAPROP , CYCLEMAXTm, CYCLOHEXYL ETHYL ACETATE, DAMASCOL,
DELTA DAMASCONE, DIHYDRO CYCLACET, DIHYDRO MYRCENOL,
DIHYDRO TERPINEOL, DIHYDRO TERPINYL ACETATE, DIMETHYL
CYCLORMOL, DIMETHYL OCTANOL PQ, DIMYRCETOL, DIOLA, DIPENTENE,
DULCINYL RECRYSTALLIZED, ETHYL-3-PHENYL GLYCIDATE,
FLEURAMONE, FLEURANIL, FLORAL SUPER, FLORALOZONE, FLORIFFOL,
FRAISTONE, FRUCTONE, GALAXOLIDE 50, GALAXOLIDE 50 BB,
GALAXOLIDE 50 IPM, GALAXOLIDE UNDILUTED, GALBASCONE,
GERALDEHYDE, GERANIOL 5020, GERANIOL 600 TYPE, GERANIOL 950,
GERANIOL 980 (PURE), GERANIOL CFT COEUR, GERANIOL COEUR,
GERANYL ACETATE COEUR, GERANYL ACETATE, PURE, GERANYL
FORMATE, GRISALVA, GUAIYL ACETATE, HELIONALTm, HERBAC,
HERBALIMETm, HEXADECANOLIDE, HEXALON, HEXENYL SALICYLATE CIS
3-, HYACINTH BODY, HYACINTH BODY NO. 3, HYDRATROPIC
ALDEHYDE.DMA, HYDROXYOL, INDOLAROME, INTRELEVEN ALDEHYDE,
INTRELEVEN ALDEHYDE SPECIAL, IONONE ALPHA, IONONE BETA, ISO
CYCLO CITRAL, ISO CYCLO GERANIOL, ISO E SUPER , ISOBUTYL
QUINOLINE, JASMALõ JESSEMAL , KHARISMAL , KHARISMAL SUPER,
KHUSINIL, KOAVONE , KOHINOOL , LIFT AROMETm, LIMOXAL,
LINDENOLTm, LYRAL , LYRAME SUPER, MANDARIN ALD 10% TRI ETH,
CITR, MARITIMA, MCK CHINESE, MELTIFITm, MELAFLEUR, MELOZONE,
METHYL ANTHRANILATE, METHYL IONONE ALPHA EXTRA, METHYL
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IONONE GAMMA A, METHYL IONONE GAMMA COEUR, METHYL IONONE
GAMMA PURE, METHYL LAVENDER KETONE, MONTAVERDI , MUGUESIA,
MUGUET ALDEHYDE 50, MUSK Z4, MYRAC ALDEHYDE, MYRCENYL
ACETATE, NECTARATETm, NEROL 900, NERYL ACETATE, OCIMENE,
OCTACETAL, ORANGE FLOWER ETHER, ORIVONE, ORRINIFF 25%,
OXASPIRANE, OZOFLEUR, PAMPLEFLEUR , PEOMOSA, PHENOXANOL ,
PICONIA, PRECYCLEMONE B, PRENYL ACETATE, PRISMANTOL, RESEDA
BODY, ROSALVA, ROSAMUSK, SANJINOL, SANTALIFFTm, SYVERTAL,
TERPINEOL,TERPINOLENE 20, TERPINOLENE 90 PQ, TERPINOLENE RECT.,
TERPINYL ACETATE, TERPINYL ACETATE JAX, TETRAHYDRO, MUGUOL ,
TETRAHYDRO MYRCENOL, TETRAMERAN, TIMBERSILKTm, TOBACAROL,
TRIMOFIX 0 TT, TRIPLAL , TRISAMBER , VANORIS, VERDOXTm,
VERDOXTm HC, VERTENEX , VERTENEX HC, VERTOFIX COEUR,
VERTOLIFF, VERTOLIFF ISO, VIOLIFF, VIVALDIE, ZENOLIDE, ABS INDIA 75
PCT MIGLYOL, ABS MOROCCO 50 PCT DPG, ABS MOROCCO 50 PCT TEC,
ABSOLUTE FRENCH, ABSOLUTE INDIA, ABSOLUTE MD 50 PCT BB,
ABSOLUTE MOROCCO, CONCENTRATE PG, TINCTURE 20 PCT, AMBERGRIS,
AMBRETTE ABSOLUTE, AMBRETTE SEED OIL, ARMOISE OIL 70 PCT
THUYONE, BASIL ABSOLUTE GRAND VERT, BASIL GRAND VERT ABS MD,
BASIL OIL GRAND VERT, BASIL OIL VERVEINA, BASIL OIL VIETNAM, BAY
OIL TERPENELESS, BEESWAX ABS N G, BEESWAX ABSOLUTE, BENZOIN
RESINOID SIAM, BENZOIN RESINOID SIAM 50 PCT DPG, BENZOIN RESINOID
SIAM 50 PCT PG, BENZOIN RESINOID SIAM 70.5 PCT TEC, BLACKCURRANT
BUD ABS 65 PCT PG, BLACKCURRANT BUD ABS MD 37 PCT TEC,
BLACKCURRANT BUD ABS MIGLYOL, BLACKCURRANT BUD ABSOLUTE
BURGUNDY, BOIS DE ROSE OIL, BRAN ABSOLUTE, BRAN RESINOID,
BROOM ABSOLUTE ITALY, CARDAMOM GUATEMALA CO2 EXTRACT,
CARDAMOM OIL GUATEMALA, CARDAMOM OIL INDIA, CARROT HEART,
CASSIE ABSOLUTE EGYPT, CASSIE ABSOLUTE MD 50 PCT IPM, CASTOREUM
ABS 90 PCT TEC, CASTOREUM ABS C 50 PCT MIGLYOL, CASTOREUM
ABSOLUTE, CASTOREUM RESINOID, CASTOREUM RESINOID 50 PCT DPG,
CEDROL CEDRENE, CEDRUS ATLANTICA OIL REDIST, CHAMOMILE OIL
ROMAN, CHAMOMILE OIL WILD, CHAMOMILE OIL WILD LOW LIMONENE,
CINNAMON BARK OIL CEYLAN, CISTE ABSOLUTE, CISTE ABSOLUTE
COLORLESS, CITRONELLA OIL ASIA IRON FREE, CIVET ABS 75 PCT PG,
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CIVET ABSOLUTE, CIVET TINCTURE 10 PCT, CLARY SAGE ABS FRENCH
DECOL, CLARY SAGE ABSOLUTE FRENCH, CLARY SAGE C'LESS 50 PCT PG,
CLARY SAGE OIL FRENCH, COPAIBA BALSAM, COPAIBA BALSAM OIL,
CORIANDER SEED OIL, CYPRESS OIL, CYPRESS OIL ORGANIC, DAVANA OIL,
GALBANOL, GALBANUM ABSOLUTE COLORLESS, GALBANUM OIL,
GALBANUM RESINOID, GALBANUM RESINOID 50 PCT DPG, GALBANUM
RESINOID HERCOLYN BHT, GALBANUM RESINOID TEC BHT, GENTIANE
ABSOLUTE MD 20 PCT BB, GENTIANE CONCRETE, GERANIUM ABS EGYPT
MD, GERANIUM ABSOLUTE EGYPT, GERANIUM OIL CHINA, GERANIUM OIL
EGYPT, GINGER OIL 624, GINGER OIL RECTIFIED SOLUBLE, GUAIAC WOOD
HEART, HAY ABS MD 50 PCT BB, HAY ABSOLUTE, HAY ABSOLUTE MD 50
PCT TEC, HEALINGWOOD, HYSSOP OIL ORGANIC, IMMORTELLE ABS YUGO
MD 50 PCT TEC, IMMORTELLE ABSOLUTE SPAIN, IMMORTELLE ABSOLUTE
YUGO, JASMIN ABS INDIA MD, JASMIN ABSOLUTE EGYPT, JASMIN
ABSOLUTE INDIA, ASMIN ABSOLUTE MOROCCO, JASMIN ABSOLUTE
SAMBAC, JONQUILLE ABS MD 20 PCT BB, JONQUILLE ABSOLUTE France,
JUNIPER BERRY OIL FLG, JUNIPER BERRY OIL RECTIFIED SOLUBLE,
LABDANUM RESINOID 50 PCT TEC, LABDANUM RESINOID BB, LABDANUM
RESINOID MD, LABDANUM RESINOID MD 50 PCT BB, LAVANDIN ABSOLUTE
H, LAVANDIN ABSOLUTE MD, LAVANDIN OIL ABRIAL ORGANIC,
LAVANDIN OIL GROSSO ORGANIC, LAVANDIN OIL SUPER, LAVENDER
ABSOLUTE H, LAVENDER ABSOLUTE MD, LAVENDER OIL COUMARIN
FREE, LAVENDER OIL COUMARIN FREE ORGANIC, LAVENDER OIL
MAILLETTE ORGANIC, LAVENDER OIL MT, MACE ABSOLUTE BB,
MAGNOLIA FLOWER OIL LOW METHYL EUGENOL, MAGNOLIA FLOWER
OIL, MAGNOLIA FLOWER OIL MD, MAGNOLIA LEAF OIL, MANDARIN OIL
MD, MANDARIN OIL MD BHT, MATE ABSOLUTE BB, MOSS TREE ABSOLUTE
MD TEX IFRA 43, MOSS-OAK ABS MD TEC IFRA 43, MOSS-OAK ABSOLUTE
IFRA 43, MOSS-TREE ABSOLUTE MD IPM IFRA 43, MYRRH RESINOID BB,
MYRRH RESINOID MD, MYRRH RESINOID TEC, MYRTLE OIL IRON FREE,
MYRTLE OIL TUNISIA RECTIFIED, NARCISSE ABS MD 20 PCT BB, NARCISSE
ABSOLUTE FRENCH, NEROLI OIL TUNISIA, NUTMEG OIL TERPENELESS,
OEILLET ABSOLUTE, OLIBANUM RESINOID, OLIBANUM RESINOID BB,
OLIBANUM RESINOID DPG, OLIBANUM RESINOID EXTRA 50 PCT DPG,
OLIBANUM RESINOID MD, OLIBANUM RESINOID MD 50 PCT DPG,

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OLIBANUM RESINOID TEC, OPOPONAX RESINOID TEC, ORANGE BIGARADE
OIL MD BHT, ORANGE BIGARADE OIL MD SCFC, ORANGE FLOWER
ABSOLUTE TUNISIA, ORANGE FLOWER WATER ABSOLUTE TUNISIA,
ORANGE LEAF ABSOLUTE, ORANGE LEAF WATER ABSOLUTE TUNISIA,
ORRIS ABSOLUTE ITALY, ORRIS CONCRETE 15 PCT IRONE, ORRIS
CONCRETE 8 PCT IRONE, ORRIS NATURAL 15 PCT IRONE 4095C, ORRIS
NATURAL 8 PCT IRONE 2942C, ORRIS RESINOID, OSMANTHUS ABSOLUTE,
OSMANTHUS ABSOLUTE MD 50 PCT BB, PATCHOULI HEART N 3,
PATCHOULI OIL INDONESIA, PATCHOULI OIL INDONESIA IRON FREE,
PATCHOULI OIL INDONESIA MD, PATCHOULI OIL REDIST, PENNYROYAL
HEART, PEPPERMINT ABSOLUTE MD, PETITGRAIN BIGARADE OIL TUNISIA,
PETITGRAIN CITRONNIER OIL, PETITGRAIN OIL PARAGUAY TERPENELESS,
PETITGRAIN OIL TERPENELESS STAB, PIMENTO BERRY OIL, PIMENTO LEAF
OIL, RHODINOL EX GERANIUM CHINA, ROSE ABS BULGARIAN LOW
METHYL EUGENOL, ROSE ABS MOROCCO LOW METHYL EUGENOL, ROSE
ABS TURKISH LOW METHYL EUGENOL, ROSE ABSOLUTE, ROSE ABSOLUTE
BULGARIAN, ROSE ABSOLUTE DAMASCENA, ROSE ABSOLUTE MD, ROSE
ABSOLUTE MOROCCO, ROSE ABSOLUTE TURKISH, ROSE OIL BULGARIAN,
ROSE OIL DAMASCENA LOW METHYL EUGENOL, ROSE OIL TURKISH,
ROSEMARY OIL CAMPHOR ORGANIC, ROSEMARY OIL TUNISIA,
SANDALWOOD OIL INDIA, SANDALWOOD OIL INDIA RECTIFIED,
SANTALOL, SCHINUS MOLLE OIL, ST JOHN BREAD TINCTURE 10 PCT,
STYRAX RESINOID, STYRAX RESINOID, TAGETE OIL, TEA TREE HEART,
TONKA BEAN ABS 50 PCT SOLVENTS, TONKA BEAN ABSOLUTE, TUBEROSE
ABSOLUTE INDIA, VETIVER HEART EXTRA, VETIVER OIL HAITI, VETIVER
OIL HAITI MD, VETIVER OIL JAVA, VETIVER OIL JAVA MD, VIOLET LEAF
ABSOLUTE EGYPT, VIOLET LEAF ABSOLUTE EGYPT DECOL, VIOLET LEAF
ABSOLUTE FRENCH, VIOLET LEAF ABSOLUTE MD 50 PCT BB, WORMWOOD
OIL TERPENELESS, YLANG EXTRA OIL, YLANG III OIL and combinations of
these.
[00182] The colorants can be among those listed in the Color Index
International by
the Society of Dyers and Colourists. Colorants include dyes and pigments and
include
those commonly used for coloring textiles, paints, inks and inkjet inks. Some
colorants
that can be utilized include carotenoids, arylide yellows, diarylide yellows,
B-naphthols,
naphthols, benzimidazolones, disazo condensation pigments, pyrazolones, nickel
azo
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yellow, phthalocyanines, quinacridones, perylenes and perinones, isoindolinone
and
isoindoline pigments, triarylcarbonium pigments, diketopyrrolo-pyrrole
pigments,
thioindigoids. Cartenoids include, for example, alpha-carotene, beta-carotene,
gamma-
carotene, lycopene, lutein and astaxanthin, Annatto extract, Dehydrated beets
(beet
powder), Canthaxanthin, Caramel, 3-Apo-8'-carotenal, Cochineal extract,
Carmine,
Sodium copper chlorophyllin, Toasted partially defatted cooked cottonseed
flour,
Ferrous gluconate, Ferrous lactate, Grape color extract, Grape skin extract
(enocianina),
Carrot oil, Paprika, Paprika oleoresin, Mica-based pearlescent pigments,
Riboflavin,
Saffron, Titanium dioxide, Tomato lycopene extract; tomato lycopene
concentrate,
Turmeric, Turmeric oleoresin, FD&C Blue No. 1, FD&C Blue No. 2, FD&C Green No.
3, Orange B, Citrus Red No. 2, FD&C Red No. 3, FD&C Red No. 40, FD&C Yellow
No. 5, FD&C Yellow No. 6, Alumina (dried aluminum hydroxide), Calcium
carbonate,
Potassium sodium copper chlorophyllin (chlorophyllin-copper complex),
Dihydroxyacetone, Bismuth oxychloride, Ferric ammonium ferrocyanide, Ferric
ferrocyanide, Chromium hydroxide green, Chromium oxide greens, Guanine,
Pyrophyllite, Talc, Aluminum powder, Bronze powder, Copper powder, Zinc oxide,
D&C Blue No. 4, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8, D&C
Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 11, FD&C
Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21, D&C
Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31,
D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, D&C Red No. 39, D&C Violet
No. 2, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow
No. 10, D&C Yellow No. 11, D&C Black No. 2, D&C Black No. 3 (3), D&C Brown No.
1, Ext. D&C, Chromium-cobalt-aluminum oxide, Ferric ammonium citrate,
Pyrogallol,
Logwood extract, 1,4-Bis[(2-hydroxy-ethyl)amino]-9,10-anthracenedione bis(2-
propenoic)ester copolymers, 1,4-Bis [(2-methylphenyl)amino] -9,10-
anthracenedione,
1,4-Bis114- (2-methacryloxyethyl) phenylamino] anthraquinone copolymers,
Carbazole
violet, Chlorophyllin-copper complex, Chromium-cobalt-aluminum oxideõ C.I. Vat
Orange 1, 2-[[2,5-Diethoxy- 4-[(4-methylphenyl)thiol] phenyl]azo] -1,3,5-
benzenetriol,
16,23-Dihydrodinaphtho [2,3-a:2',3'-i] naphth 112,3:6,71 indolo [2,3-c]
carbazole-
5,10,15,17,22,24-hexone, N,N'-(9,10-Dihydro- 9,10-dioxo- 1,5-anthracenediy1)
bisbenzamide, 7,16-Dichloro- 6,15-dihydro- 5,9,14,18-anthrazinetetrone, 16,17-
Dimethoxydinaphtho (1,2,3-cd:3',2',1'-lm) perylene-5,10-dione,
Poly(hydroxyethyl
methacrylate) -dye copolymers(3), Reactive Black 5, Reactive Blue 21, Reactive
Orange
78, Reactive Yellow 15, Reactive Blue No. 19, Reactive Blue No. 4, C.I.
Reactive Red
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11, C.I. Reactive Yellow 86, C.I. Reactive Blue 163, C.I. Reactive Red 180,
44(2,4-
dimethylphenyl)azol- 2,4-dihydro- 5-methyl-2-phenyl- 3H-pyrazol-3-one (solvent
Yellow 18), 6-Ethoxy-2- (6-ethoxy-3-oxobenzolbl thien-2(3H)- ylidene)
benzolblthiophen- 3(2H)-one, Phthalocyanine green, Vinyl alcohol/methyl
methacrylate-
dye reaction products, C.I. Reactive Red 180, C.I. Reactive Black 5, C.I.
Reactive
Orange 78, C.I. Reactive Yellow 15, C.I. Reactive Blue 21, Disodium 1-amino-
44144(2-
bromo-1-oxoally0aminol-2-sulphonatophenyllamino1-9,10-dihydro-9,10-
dioxoanthracene-2-sulphonate (Reactive Blue 69), D&C Blue No. 9,
1Phthalocyaninato(2-)1 copper and mixtures of these.
[00183] Other than in the examples herein, or unless otherwise expressly
specified, all
of the numerical ranges, amounts, values and percentages, such as those for
amounts of
materials, elemental contents, times and temperatures of reaction, ratios of
amounts, and
others, in the following portion of the specification and attached claims may
be read as if
prefaced by the word "about" even though the term "about" may not expressly
appear
with the value, amount, or range. Accordingly, unless indicated to the
contrary, the
numerical parameters set forth in the following specification and attached
claims are
approximations that may vary depending upon the desired properties sought to
be
obtained by the present invention. At the very least, and not as an attempt to
limit the
application of the doctrine of equivalents to the scope of the claims, each
numerical
parameter should at least be construed in light of the number of reported
significant
digits and by applying ordinary rounding techniques.
[00184] Notwithstanding that the numerical ranges and parameters setting forth
the
broad scope of the invention are approximations, the numerical values set
forth in the
specific examples are reported as precisely as possible. Any numerical value,
however,
inherently contains error necessarily resulting from the standard deviation
found in its
underlying respective testing measurements. Furthermore, when numerical ranges
are
set forth herein, these ranges are inclusive of the recited range end points
(e.g., end
points may be used). When percentages by weight are used herein, the numerical
values
reported are relative to the total weight.
[00185] Also, it should be understood that any numerical range recited herein
is
intended to include all sub-ranges subsumed therein. For example, a range of
"1 to 10"
is intended to include all sub-ranges between (and including) the recited
minimum value
of 1 and the recited maximum value of 10, that is, having a minimum value
equal to or
greater than 1 and a maximum value of equal to or less than 10. The terms
"one," "a," or
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"an" as used herein are intended to include "at least one" or "one or more,"
unless
otherwise indicated.
[00186] Any patent, publication, or other disclosure material, in whole or in
part, that
is said to be incorporated by reference herein is incorporated herein only to
the extent
that the incorporated material does not conflict with existing definitions,
statements, or
other disclosure material set forth in this disclosure. As such, and to the
extent
necessary, the disclosure as explicitly set forth herein supersedes any
conflicting material
incorporated herein by reference. Any material, or portion thereof, that is
said to be
incorporated by reference herein, but which conflicts with existing
definitions,
statements, or other disclosure material set forth herein will only be
incorporated to the
extent that no conflict arises between that incorporated material and the
existing
disclosure material.
[00187] While this invention has been particularly shown and described with
references to preferred embodiments thereof, it will be understood by those
skilled in the
art that various changes in form and details may be made therein without
departing from
the scope of the invention encompassed by the appended claims.
59

Representative Drawing